CN110879223A - Rapid detection reagent and detection method for formaldehyde in beer - Google Patents

Rapid detection reagent and detection method for formaldehyde in beer Download PDF

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Publication number
CN110879223A
CN110879223A CN201911144119.5A CN201911144119A CN110879223A CN 110879223 A CN110879223 A CN 110879223A CN 201911144119 A CN201911144119 A CN 201911144119A CN 110879223 A CN110879223 A CN 110879223A
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solution
silver
formaldehyde
reagent
gold
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郭志勇
董静
张晨
黄桂华
陈曦
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Xiamen Huaxia University
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Xiamen Huaxia University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering

Abstract

The invention discloses a rapid detection reagent for formaldehyde in beer, which comprises gold nano-sol and silver ammonia solution, wherein the reagent reacts with formaldehyde to generate gold-silver composite nano-particles, and the gold-silver composite nano-particles are of a gold-core-silver-shell structure. The invention also discloses a method for rapidly detecting formaldehyde in beer by adopting the reagent. The invention can realize the rapid detection of formaldehyde in beer, has simple method and low Raman background interference, and is easy to popularize and use.

Description

Rapid detection reagent and detection method for formaldehyde in beer
Technical Field
The invention relates to formaldehyde (CH)3CHO) detection technology, in particular to a rapid detection reagent for formaldehyde in beer and a detection method thereof.
Background
The beer is a beverage with sedative activity, refreshing property, attractive fragrance and classic bitter taste. However, during storage, the freshness of beer is gradually reduced, accompanied by deterioration in taste, formation of smoke, enzymatic browning, and the like. Thus, the formaldehyde in beer may originate from natural production and artificial addition during fermentation to increase the freshness of the product and reduce unwanted products. Formaldehyde may cause respiratory tract inflammation, headache, nausea, lethargy and strong allergic reaction, so the identification and content determination of formaldehyde in beer are of interest. Researchers develop a series of analysis methods for detecting formaldehyde in beer, mainly including high performance liquid chromatography, fluorescence method, gas chromatography, mass spectrometry, Raman spectrometry and the like.
The Raman spectroscopy is a relatively quick and convenient detection method, is widely applied to detection of substances such as sulfite, heavy metal ions, organic matter residues and the like in wine, and has the core technology of development of a substrate signal enhancement material. Researchers have developed substrates such as noble metal substrates, thin-layer metal substrates, and three-dimensional nanomaterials decorated with metal particles for raman signal enhancement. However, the substrate is usually accompanied by the disadvantages of low stability, non-uniformity of metal particles, etc., which greatly limits the qualitative and quantitative analysis of raman spectroscopy. In order to improve the accuracy of the method, an internal standard is often required to be introduced into a Raman detection system or data analysis and correction are carried out, and the current research results show that the method cannot achieve satisfactory effects. Therefore, the development of novel Raman signal enhancement substrate materials and methods and the establishment of an efficient and accurate formaldehyde detection system have important significance for the rapid detection of formaldehyde in beer.
Disclosure of Invention
The invention aims to provide a reagent and a method for rapidly detecting formaldehyde in beer, aiming at overcoming the defects in the prior art, the reagent and the method can be used for rapidly detecting formaldehyde in beer, are simple and convenient, have low Raman background interference and are easy to popularize and use.
Therefore, the invention adopts the following technical scheme:
a reagent for rapidly detecting formaldehyde in beer comprises gold nano-sol and silver ammonia solution, wherein the reagent reacts with formaldehyde to generate gold-silver composite nano-particles, and the gold-silver composite nano-particles are of a gold-core-silver-shell structure.
Preferably, the preparation method comprises the following steps:
s11, preparing gold nano sol, namely heating a chloroauric acid solution to slight boiling, then adding a trisodium citrate solution under vigorous stirring, reacting under the slight boiling state, naturally cooling to room temperature, and finally adding ultrapure water to dilute to obtain the gold nano sol;
s12, preparing a silver-ammonia solution, namely dropwise adding ammonia water into a silver nitrate solution while oscillating until the initially generated precipitate is just dissolved, then adding a sodium hydroxide solution, and finally adding ultrapure water to dilute to obtain the silver-ammonia solution;
s13, preparing a rapid detection reagent for formaldehyde in beer, and uniformly mixing the gold nano sol, the silver ammonia solution and ultrapure water to obtain the rapid detection reagent for formaldehyde in beer.
More preferably, in the step S11, the mass fraction of the chloroauric acid in the chloroauric acid solution is 0.01% to 0.05%, the volume of the chloroauric acid solution is 10 to 200mL, the mass fraction of the trisodium citrate in the trisodium citrate solution is 1% to 5%, the volume of the trisodium citrate solution is 1 to 10mL, the reaction time is 10 to 60min, and the dilution factor is 1.5 to 3.
Still further preferably, in the step S12, the silver nitrate solution, the ammonia water and the sodium hydroxide solution are added at the following molar concentrations: 0.1-0.5 mol/L silver nitrate solution, 0.2-1 mol/L ammonia water and 0.1-5 mol/L sodium hydroxide solution, and the dilution times are 5-8.
Still more preferably, in the step S13, the gold nano sol, the silver ammonia solution and ultrapure water are added in the following volumes: 50-200 mu L of gold nano sol, 50-200 mu L of silver ammonia solution and 500-1000 mu L of ultrapure water.
A method for rapidly detecting formaldehyde in beer by adopting the reagent comprises the following steps:
s21, adding the reagent and the sample solution to be detected into a sample bottle, mixing uniformly, sealing the sample bottle, and carrying out constant temperature reaction;
and S22, cooling the sample bottle to room temperature, respectively adding a p-aminophenol solution and a potassium chloride solution, uniformly mixing, and performing Raman spectrum determination. Each sample solution to be tested is tested for three times, and the final result is based on the average value of the three measurements.
Preferably, in the step S21, the mass concentration of the formaldehyde in the added sample solution to be tested is 0.1-55 g/mL.
Preferably, in the step S21, the volume of the sample solution to be tested is 10 to 100 μ L, the temperature of the isothermal reaction is 10 to 100 ℃, and the time is 5 to 60 min.
Preferably, in the step S22, the molar concentration of the p-aminophenol solution is 10-4~10-1The volume of the potassium chloride solution is 10-100 mu L, the molar concentration of the potassium chloride solution is 0.1-1 mol/L, and the volume of the potassium chloride solution is 10-100 mu L.
Preferably, in step S22, the raman spectroscopy measurement conditions are: the laser wavelength is 585-785 nm, and the signal integration time is 1-5 s.
The technical scheme has the advantages that: gold nanoparticles are added in the reaction of formaldehyde and silver ammonia solution to serve as crystal seeds to form gold-silver composite nanoparticles, so that the Raman signal enhancement effect is realized, and the rapid detection of formaldehyde in beer can be realized.
Drawings
FIG. 1 is a transmission electron micrograph of gold nanoparticles of example seven;
FIG. 2 is a transmission electron micrograph of silver nanoparticles of example VII;
FIG. 3 is a transmission electron micrograph (100nm) of the gold and silver composite nanoparticles of example VII;
FIG. 4 is a transmission electron micrograph (20nm) of the gold and silver composite nanoparticles of example VII;
FIG. 5 is an EDS energy spectrum of gold element of example VIII;
FIG. 6 is an EDS energy spectrum of elemental silver of example eight;
FIG. 7 is a Raman spectrum of example nine;
FIG. 8 is a UV spectrum of example ten;
FIG. 9 is a graph of the intensity of the surface-enhanced Raman signal of EXAMPLE eleven;
FIG. 10 is a surface enhanced Raman spectrum of example twelve;
FIG. 11 is a plot of the surface enhanced Raman signal intensity of the thirteenth example;
FIG. 12 is a graph of the intensity of the surface enhanced Raman signal of the fourteenth embodiment.
Detailed Description
In order that the objects, features and advantages of the invention will be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings, which are illustrated in detail in order to provide a thorough understanding of the invention, but which may be carried out in other ways than those described. Accordingly, the invention is not limited by the specific implementations disclosed below.
Example one
The embodiment provides a reagent for rapidly detecting formaldehyde in beer, and the preparation method comprises the following steps:
s1, preparing gold nanoparticles. Adding 100mL of 0.01% chloroauric acid solution into a round-bottom flask, heating to slight boiling, then adding 1mL of 1% trisodium citrate solution under vigorous stirring, reacting for 30min under slight boiling state, then naturally cooling to room temperature, and finally adding 101mL of ultrapure water to dilute to obtain the gold nano sol.
S2, preparing a silver ammonia solution. 500 mu L of 0.5mol/L silver nitrate solution and 520 mu L of 1mol/L ammonia water are sequentially added into a test tube, and 325 mu L of 3mol/L sodium hydroxide solution and 8.66mL ultrapure water are sequentially added after shaking up to obtain the silver-ammonia solution.
S3, and preparing a rapid detection reagent for formaldehyde in beer. Adding 750 mu L of ultrapure water, 100 mu L of gold nano-sol and 100 mu L of silver ammonia solution into a sample bottle, and uniformly mixing to obtain the rapid detection reagent for formaldehyde in beer.
Example two
The embodiment provides a reagent for rapidly detecting formaldehyde in beer, and the preparation method comprises the following steps:
s1, preparing gold nanoparticles. Adding 10mL of 0.05% chloroauric acid solution into a round-bottom flask, heating to slight boiling, then adding 10mL of 2% trisodium citrate solution under vigorous stirring, reacting for 10min under slight boiling state, naturally cooling to room temperature, and finally adding 40mL of ultrapure water to dilute to obtain the gold nano sol.
S2, preparing a silver ammonia solution. 400 mu L of 0.1mol/L silver nitrate solution and 815 mu L of 0.1mol/L ammonia water are sequentially added into a test tube, after shaking up, 30 mu L of 5mol/L sodium hydroxide solution and 4.98mL ultrapure water are sequentially added to obtain the silver-ammonia solution.
S3, and preparing a rapid detection reagent for formaldehyde in beer. And adding 1000 mu L of ultrapure water, 200 mu L of gold nano-sol and 200 mu L of silver ammonia solution into the sample bottle, and uniformly mixing to obtain the rapid detection reagent for formaldehyde in beer.
EXAMPLE III
The embodiment provides a reagent for rapidly detecting formaldehyde in beer, and the preparation method comprises the following steps:
s1, preparing gold nanoparticles. Adding 200mL of 0.03% chloroauric acid solution into a round-bottom flask, heating to slight boiling, then adding 2mL of 5% trisodium citrate solution under vigorous stirring, reacting for 60min under slight boiling state, naturally cooling to room temperature, and finally adding 101mL of ultrapure water to dilute to obtain the gold nano sol.
S2, preparing a silver ammonia solution. 200 mu L of 0.2mol/L silver nitrate solution and 830 mu L of 0.5mol/L ammonia water are sequentially added into a test tube, after shaking up, 70 mu L of 4mol/L sodium hydroxide solution and 5.5mL ultrapure water are sequentially added to obtain the silver-ammonia solution.
S3, and preparing a rapid detection reagent for formaldehyde in beer. And adding 500 mu L of ultrapure water, 280 mu L of gold nano-sol and 300 mu L of silver ammonia solution into the sample bottle, and uniformly mixing to obtain the rapid detection reagent for formaldehyde in beer.
Example four
The embodiment provides a method for rapidly detecting formaldehyde in beer by using the reagent prepared in the first embodiment, which comprises the following steps:
s21, adding 950 mu L of the reagent prepared in the first embodiment and 50 mu L of the sample solution to be detected into a sample bottle, mixing uniformly, sealing the sample bottle, and reacting at constant temperature of 70 ℃ for 10 min.
S22, cooling the sample bottle to room temperature, and adding 100 mu L10-4mol/L of para-ammoniaThe phenylthiophenol solution and 100 mu L of 0.1mol/L potassium chloride solution are mixed evenly and poured into a quartz colorimetric pool for Raman spectrum determination. The conditions for raman spectroscopy were: the laser wavelength was 585nm and the signal integration time 1 s. Each sample solution to be tested is tested for three times, and the final result is based on the average value of the three measurements.
EXAMPLE five
The embodiment provides a method for rapidly detecting formaldehyde in beer by using the reagent prepared in the first embodiment, which comprises the following steps:
s21, adding 900 mu L of the reagent prepared in the embodiment I and 100 mu L of the sample solution to be detected into a sample bottle, mixing uniformly, sealing the sample bottle, and reacting at constant temperature of 10 ℃ for 60 min.
S22, returning the sample bottle to room temperature, respectively adding 50 mu L of 0.01mol/L p-aminophenol solution and 50 mu L of 0.1mol/L potassium chloride solution, uniformly mixing, and pouring into a quartz cuvette for Raman spectrum measurement. The conditions for raman spectroscopy were: the laser wavelength was 685nm and the signal integration time was 3 s. Each sample solution to be tested is tested for three times, and the final result is based on the average value of the three measurements.
EXAMPLE six
The embodiment provides a method for rapidly detecting formaldehyde in beer by using the reagent prepared in the first embodiment, which comprises the following steps:
s21, adding 920 mu L of the reagent prepared in the embodiment I and 80 mu L of the sample solution to be detected into a sample bottle, mixing uniformly, sealing the sample bottle, and reacting at constant temperature of 100 ℃ for 50 min.
S22, cooling the sample bottle to room temperature, respectively adding 10 mu L of 0.1mol/L p-aminophenol solution and 10 mu L of 1mol/L potassium chloride solution, mixing uniformly, and pouring into a quartz cuvette for Raman spectrum determination. The conditions for raman spectroscopy were: the laser wavelength was 785nm and the signal integration time was 5 s. Each sample solution to be tested is tested for three times, and the final result is based on the average value of the three measurements.
Formaldehyde can take place the toronto reaction with silver ammonia solution and generate silver nanoparticle, though silver nanoparticle is comparatively the raman signal reinforcing material who uses always, its raman signal reinforcing effect not only often is less than, can receive the great influence of formaldehyde solution concentration moreover, is unfavorable for stable signal output.
The gold and silver composite nanoparticles (Au @ AgNPs) are also a material capable of effectively enhancing Raman signals, have stronger electromagnetic properties compared with pure silver nanoparticles, are simple and convenient in synthesis method, have long-term stability and optical response characteristics, and can achieve continuous and stable Raman signal enhancement effect.
Therefore, the gold nanoparticles are introduced into the Torren reaction as seed crystals by adopting an in-situ polymerization method, and the silver nanoshell is induced to be generated on the surface of the gold nanoparticles, so that the gold-silver composite nanoparticle material with a typical core-shell structure is formed. Under the condition of existence of seed crystal, the material can be synthesized quickly. The introduction of the gold nanoparticles can not only increase the stability of the material, but also increase the photoresponse characteristic of the material. Aiming at formaldehyde solutions with different concentrations, the formed gold-silver composite nano-particle material can greatly enhance Raman signals, has convenient sensing characteristics, and can be used for quickly detecting formaldehyde.
Comparative example
And synthesizing the silver nanoparticles by a tolan reaction in the absence of the gold nanoparticles.
S1, preparing silver ammonia solution as the step S2 in the first embodiment.
S2, adding 100 mu L of silver ammonia solution, 850 mu L of ultrapure water and 50 mu L of 10g/mL formaldehyde solution into the sample bottle in sequence. Wherein the mass concentration of the formaldehyde solution can be titrated by an indirect iodometry method. The sample bottle was sealed and placed in a thermostat to react at 70 ℃ for 10 min. And obtaining the gold and silver composite nano particles.
EXAMPLE seven
In order to observe the change of the shape and structure of the gold and silver nanoparticles before and after the tolen reaction, the transmission electron microscope characterization is performed on the shapes of the gold nanoparticles synthesized in the first embodiment, the silver nanoparticles synthesized in the comparative example and the gold and silver composite nanoparticles synthesized by the method in the fourth embodiment when the mass concentration of formaldehyde in the sample solution to be detected is 10 g/mL. As shown in fig. 1, the gold nanoparticles are around 10nm, and as shown in fig. 2, the silver nanoparticles are around 5nm in size. As shown in fig. 3 and 4, fig. 4 is an enlarged view of fig. 3, and the size of the gold-silver composite nano-particles is about 30nm and is a core-shell structure.
Example eight
In order to observe the change of the shape and structure of the gold and silver nanoparticles before and after the toleren reaction, the gold and silver composite nanoparticles described in the seventh embodiment were subjected to element component characterization. As shown in fig. 5 and 6, it can be inferred from the element area size in the figures that the silver nanoparticles are modified on the outer surface of the gold nanoparticles.
Example nine
In order to examine the optimal sensing performance of the reagent of the present invention, the surface enhanced raman signals of the gold nanoparticles, silver nanoparticles and gold-silver composite nanoparticles described in example seven were compared. As shown in FIG. 7, the gold-silver composite nano-particle material is in the range of 1148cm-1The surface enhanced Raman signal is obviously increased and can be used as an effective peak for tracing the reagent.
Example ten
Ultraviolet absorption signals of the gold nanoparticles and the gold and silver composite nanoparticles described in example seven were compared. As shown in fig. 8, the surface plasmon resonance response (LSPR) peak of gold nanoparticles in the gold and silver composite nanoparticles is changed from 520nm to 410nm, which not only proves that the composite nanoparticles are successfully synthesized, but also improves the raman signal enhancement effect.
EXAMPLE eleven
Reproducibility experiments are key factors in investigating whether materials can be used in practical applications. When the mass concentration of the formaldehyde in the sample solution to be detected is 10g/mL, 15 times of Raman signal acquisition is carried out by adopting the method described in the fourth embodiment, and the observation is carried out at 1148cm-1The surface of (a) enhances the raman signal. As shown in FIG. 9, it was found that the relative standard deviation of the measurement using the reagent of the present invention was within 7.1%.
Example twelve
In order to investigate the application performance of the gold-silver composite nano-particle material synthesized by the methodRaman signal collection was performed on the solid phase substrate material and the formaldehyde solutions with mass concentrations of 0.1, 0.5, 0.8, 1, 3, 8, 10, 20, 30, and 55g/mL respectively by the method described in example IV, and the mass concentration was observed at 1148cm-1The surface of (a) enhances the raman signal. As shown in fig. 10, the gold-silver composite nanoparticle material synthesized by the present embodiment has a better raman signal enhancement effect than the solid-phase substrate material.
EXAMPLE thirteen
In order to examine the linear range of the measurement by the method of the present invention, the measurement was carried out on a formaldehyde solution having a mass concentration of 0.1g/mL to 55g/mL by the method described in example IV. As shown in fig. 11, a good linear relationship was exhibited in this concentration range.
Example fourteen
To examine the selectivity of the method of the invention, common aldehydes or analogues were selected: acetaldehyde (CH)3CHO, the mass concentration in the detection system is respectively 100, 40 and 10 mug/mL), ethanol (CH)3CH2OH), diethyl ether (CH)3OCH3) Methanol (CH)3OH), acetic acid (CH)3COOH)、SO4 2-、PO4 2-、NO3 -、Ca2+、Mg2+And carrying out an interference experiment on a blank sample (blank), wherein the mass concentration of the substance to be detected in the detection system is 10 mu g/mL. As shown in fig. 12, the method of the present invention has good selectivity for the rapid sensing of formaldehyde, which is due to the following two major reasons: (1) formaldehyde can generate tollon reaction with silver ammonia solution, thereby realizing effective generation of silver ions; (2) meanwhile, under the condition that the gold nanoparticles exist, gold and silver composite nanoparticles with core-shell structures can be formed through reaction, so that the Raman signal of a detection system can be effectively enhanced, and the possibility is provided for quick sensing of formaldehyde.
Example fourteen
10 different beer samples are taken, the mass concentration of formaldehyde in the samples is measured by adopting the method and the national standard detection method respectively, and the detection data are compared, and the results are shown in table 1. The result data show that the method of the invention has better precision and can be used as a new means for quickly and simply detecting the formaldehyde in the beer.
TABLE 1 comparison of the method of the present invention with the national standard detection method for the detection data of formaldehyde in beer
Figure BDA0002281708890000101
The invention fully utilizes the reduction reaction of formaldehyde and silver ammonia solution in the water phase in the tolan reaction process, is used for detecting low-concentration formaldehyde, and simultaneously combines a rapid water distillation sample pretreatment method and a surface enhanced Raman spectroscopy technology, thereby providing a rapid detection reagent for formaldehyde in beer, which is rapid, simple and convenient, has low Raman background interference and is easy to popularize and use, and a detection method thereof.
The reagent and the method are not only applied to the rapid detection of formaldehyde in beer, but also can be applied to the detection of formaldehyde in other samples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The reagent for rapidly detecting formaldehyde in beer is characterized by comprising gold nano-sol and silver ammonia solution, wherein the reagent reacts with formaldehyde to generate gold-silver composite nano-particles, and the gold-silver composite nano-particles are of a gold-core-silver-shell structure.
2. The reagent for rapidly detecting formaldehyde in beer according to claim 1, wherein the preparation method comprises the following steps:
s11, preparing gold nano sol, namely heating a chloroauric acid solution to slight boiling, then adding a trisodium citrate solution under vigorous stirring, reacting under the slight boiling state, naturally cooling to room temperature, and finally adding ultrapure water to dilute to obtain the gold nano sol;
s12, preparing a silver-ammonia solution, namely dropwise adding ammonia water into a silver nitrate solution while oscillating until the initially generated precipitate is just dissolved, then adding a sodium hydroxide solution, and finally adding ultrapure water to dilute to obtain the silver-ammonia solution;
s13, preparing a rapid detection reagent for formaldehyde in beer, and uniformly mixing the gold nano sol, the silver ammonia solution and ultrapure water to obtain the rapid detection reagent for formaldehyde in beer.
3. The reagent of claim 2, wherein in step S11, the mass fraction of chloroauric acid in the chloroauric acid solution is 0.01-0.05%, the volume of the chloroauric acid solution is 10-200 mL, the mass fraction of trisodium citrate in the trisodium citrate solution is 1-5%, the volume of the trisodium citrate solution is 1-10 mL, the reaction time is 10-60 min, and the dilution factor is 1.5-3.
4. The reagent of claim 3, wherein in the step S12, the silver nitrate solution, the ammonia water and the sodium hydroxide solution are added at the following molar concentrations: 0.1-0.5 mol/L silver nitrate solution, 0.2-1 mol/L ammonia water and 0.1-5 mol/L sodium hydroxide solution, and the dilution times are 5-8.
5. The reagent of claim 4, wherein in step S13, the gold nanosol, the silver ammonia solution and the ultrapure water are added in the following volumes: 50-200 mu L of gold nano sol, 50-200 mu L of silver ammonia solution and 500-1000 mu L of ultrapure water.
6. A method for rapidly detecting formaldehyde in beer by using the reagent as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
s21, adding the reagent and the sample solution to be detected into a sample bottle, mixing uniformly, sealing the sample bottle, and carrying out constant temperature reaction;
and S22, cooling the sample bottle to room temperature, respectively adding a p-aminophenol solution and a potassium chloride solution, uniformly mixing, and performing Raman spectrum determination. Each sample solution to be tested is tested for three times, and the final result is based on the average value of the three measurements.
7. The method as claimed in claim 6, wherein in step S21, the mass concentration of formaldehyde in the sample solution to be tested is 0.1-55 g/mL.
8. The method for rapidly detecting formaldehyde in beer according to claim 6, wherein in the step S21, the volume of the sample solution to be detected is 10-100 μ L, the temperature of the isothermal reaction is 10-100 ℃, and the time is 5-60 min.
9. The method of claim 6, wherein in step S22, the molar concentration of the p-aminophenol solution is 10-4~10-1The volume of the potassium chloride solution is 10-100 mu L, the molar concentration of the potassium chloride solution is 0.1-1 mol/L, and the volume of the potassium chloride solution is 10-100 mu L.
10. The method as claimed in claim 6, wherein in step S22, the Raman spectroscopy is performed under the following conditions: the laser wavelength is 585-785 nm, and the signal integration time is 1-5 s.
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Application publication date: 20200313