CN108254356A - It is a kind of to be used for the method for formaldehyde and acetaldehyde field quick detection in wine - Google Patents

It is a kind of to be used for the method for formaldehyde and acetaldehyde field quick detection in wine Download PDF

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Publication number
CN108254356A
CN108254356A CN201810281700.0A CN201810281700A CN108254356A CN 108254356 A CN108254356 A CN 108254356A CN 201810281700 A CN201810281700 A CN 201810281700A CN 108254356 A CN108254356 A CN 108254356A
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formaldehyde
acetaldehyde
wine
aminophenyl
thiophenol
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CN108254356B (en
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李丹
段化珍
曹海荣
徐逍
马亚丹
邓维
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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

Abstract

The invention discloses a kind of for the method for formaldehyde and acetaldehyde field quick detection in wine.The present invention is using formaldehyde and acetaldehyde in paper substrate micro-fluidic analytical equipment μ PAD extraction edible wine samples, using p-aminophenyl thiophenol ATP as probe molecule, by the use of silver mirror reaction prepare silver nano-grain Ag NPs as Surface enhanced Raman scattering enhancing substrate, variation relation between the peak intensity of p-aminophenyl thiophenol and formaldehyde or acetaldehyde is established, and then realize the live fast quantification and qualitative detection of formaldehyde and acetaldehyde in wine sample to be measured by Portable Raman spectrometer.Compared with existing field quick detection formaldehyde, acetaldehyde method, the present invention has the characteristics that highly selective, analysis is quick, high sensitivity, amount of samples is few, has a wide range of application, is easy to operate and easy to carry.The detection limit of this method is respectively 0.0046 μM of formaldehyde, 0.0032 μM of acetaldehyde.

Description

It is a kind of to be used for the method for formaldehyde and acetaldehyde field quick detection in wine
Technical field
The invention belongs to technical field of analysis and detection, specifically, are related to a kind of fast for formaldehyde in wine and acetaldehyde scene The method of speed detection.
Background technology
Formaldehyde is gas that is a kind of colourless and having intense irritation smell, is a kind of thin with more highly toxic destruction biology The plasm poisonous substance of born of the same parents' protein can cause and shed tears, nausea, have difficulty in breathing, also the skin, respiratory tract and internal organ of people can be caused Damage, anaesthetizes the nervous centralis of people, causes pulmonary edema, hepatic coma, kidney failure etc..Because economic interests are driven, some criminals Using formaldehyde as food additives, as added in edible wine sample class beverage formaldehyde prevent it is muddy, increase transparency that these can all be caused The serious pollution of food damages health.The World Health Organization confirms that formaldehyde is allergen for teratogenesis, carcinogen, Long Term Contact will lead to gene mutation.《Food Hygiene Law of the People's Republic of China》In expressly provided and forbid formaldehyde as food Additive should not exceed national standard in formaldehyde in food content.
Acetaldehyde is the liquid of a kind of colourless easy flowing and irritant smell.Suitable acetaldehyde can be used for the hair of dairy products Ferment, available for adopting the fresh-keeping of rear garden crop, the fruit essences such as adjustable orange, orange, apple, apricot, strawberry, it can also be used to The edible wines essence such as grape wine, Rum, whiskey.Once excessive, the lighter contactee generates irritant contact dermatitis, has Eye, nose, upper respiratory tract irritation, there is nausea,vomiting,diarrhea symptom and bronchitis;There is pulmonary edema, headache, thermophilic in severe one It sleeps, the disturbance of consciousness or even liver, kidney and cardiac damage occur.The concentration of acetaldehyde in food is controlled, detects its concentration before eating, It enables people to eat healthy and safely.
At present, the detection method of formaldehyde acetaldehyde has:High performance liquid chromatography, gas chromatography, spectrophotometry, colorimetric drop Determine method.Chromatography, spectrophotometry need to analyze using large-scale instrument, are unsuitable for Site Detection, and spend higher, Check-Out Time It is long;Colorimetric titration is difficult to control, and calculating error is relatively large, is easily influenced by extraneous factor.Therefore urgently research and development are a kind of Simply, fast and accurately suitable for edible wine sample formaldehyde acetaldehyde detection method.Surface enhanced Raman scattering (SERS) is Refer to when some molecules are adsorbed to certain textured metals (Au, Ag, Cu when) surface, their Raman scattering intensities can increase 104~106Times.In recent years, since its is harmless and hypersensitization characteristic, Surface enhanced Raman scattering (SERS) has become powerful Molecular spectroscopy techniques, be widely used in food security, biological detection etc..In recent years, Chinese patent (application number CN 201410040401.X) there are the formaldehyde derivatives of Raman signal by analysis so as to quantitative analysis formaldehyde with SERS.This method sample Product must pass through phenol and handle, generation derivative, the detection of formaldehyde in comparatively laborious and inedibility wine sample.
Invention content
In order to solve the deficiency in above-mentioned prior art, show the present invention provides one kind for formaldehyde in wine and acetaldehyde The method that field is quickly detected.The present invention is made using the silver nano particle composite material (Ag NPs-ATP) of p-aminophenyl thiophenol modification For SERS active-substrate, with reference to the analytical equipment of μ-PAD, the SERS field fast detection methods based on formaldehyde acetaldehyde are established, Have the characteristics that highly selective, analysis is quick, high sensitivity, amount of samples is few, has a wide range of application, can realize in edible wine sample Formaldehyde acetaldehyde it is accurate, efficient, rapidly analyze, be expected to further apply environment and food analysis field.
The purpose of the present invention is what is be achieved through the following technical solutions:
Present invention offer is a kind of for the method for formaldehyde and acetaldehyde field quick detection in wine, uses paper substrate micro-fluidic point Formaldehyde and acetaldehyde in analysis apparatus μ-PAD extraction edible wine samples, using p-aminophenyl thiophenol ATP as probe molecule, utilize silver mirror reaction Enhancing substrates of the silver nano-grain Ag NPs of preparation as Surface enhanced Raman scattering, is established by Portable Raman spectrometer Variation relation between the peak intensity of p-aminophenyl thiophenol and formaldehyde or acetaldehyde, and then realize formaldehyde and acetaldehyde in wine sample to be measured Live fast quantification and qualitative detection.
It is a kind of to be as follows for the method for formaldehyde and acetaldehyde field quick detection in wine in the present invention:
(1) paper substrate micro-fluidic analytical equipment μ-PAD are made;
(2) silver ammino solution of the thiophenol containing p-aminophenyl is added dropwise in the area to be measured of paper substrate micro-fluidic analytical equipment μ-PAD, treated It surveys area and the standard solution containing formaldehyde and acetaldehyde separately or together is added dropwise, react 10-15min at room temperature, be prepared to ammonia The silver nano-grain Ag NPs-ATP of base benzenethiol modification, using it as SERS active-substrate, utilize Portable Raman spectrometer Surface enhanced Raman spectroscopy SERS detections are carried out to wine sample to be measured, the peak intensity and formaldehyde or acetaldehyde for establishing p-aminophenyl thiophenol contain Linear relationship between amount;
(3) wine sample alternate standard solution to be measured is prepared into SERS active-substrate by step (2), utilizes Portable Raman optical spectrum Instrument to wine sample to be measured carry out Surface enhanced Raman spectroscopy SERS detections, then compare wine sample and standard solution to be measured Raman spectrum and Linear relationship, so as to fulfill the live fast quantification and qualitative detection of formaldehyde and acetaldehyde in wine sample to be measured.
In the present invention, in step (2), the preparation method of the silver ammino solution of the thiophenol containing p-aminophenyl is as follows:Take 2~ The silver nitrate solution of 5mL0.01moL/L and the oscillation mixing of 100 μ L 0.1moL/L sodium hydrate aqueous solutions, it is faint yellow heavy to generate It forms sediment;Weak aqua ammonia is instilled dropwise, until the precipitation initially generated dissolves just, adds 50~125 μ L 1 × 10-4Pair of mol/L Aminothiophenol prepares the silver ammino solution of the thiophenol containing p-aminophenyl.
Compared with prior art, the device have the advantages that being:
1. the analytical equipment and SERS technologies by μ-PAD are combined, the formaldehyde acetaldehyde choosing in edible wine sample can be achieved at the same time Selecting property detaches and detection, which can not only eliminate the interference of background, but also can improve the detection sensitivity of formaldehyde acetaldehyde, according to Formaldehyde, acetaldehyde concentration and Raman signal intensity between linear relationship, detection limit (DL) according to 3 times measure zero standard deviations The ratio calculation of (δ) and linearity curve slope (k) obtain, i.e. DL=3 δ/k, and the detection limit that can obtain formaldehyde and acetaldehyde is respectively 0.0046 μM of formaldehyde, 0.0032 μM of acetaldehyde.
2. silver mirror reaction provides not only high SERS activity hot spots, and reactant of the formaldehyde acetaldehyde as silver mirror reaction And analyte, analytic process is simplified, reduces the interference of additional reactant;
3. due to having significant signal amplification, established paper tape is ideal detection sample, is had acceptable Stability, low cost and easy-operating feature.
Description of the drawings
Fig. 1 is the SEM figures of Ag NPs-ATP in the embodiment of the present invention.
Fig. 2 is that independent formaldehyde acetaldehyde solution enhances p-aminophenyl thiophenol liquid after silver mirror reaction occurs in the embodiment of the present invention (5×10-5Mol/L SERS collection of illustrative plates) is labeled as the TuPu method peak of p-aminophenyl thiophenol shown in figure.
Fig. 3 is that various concentration formaldehyde standard solution enhances p-aminophenyl thiophenol after silver mirror reaction occurs in the embodiment of the present invention Liquid (5 × 10-5Mol/L SERS collection of illustrative plates).
Fig. 4 is the standard concentration of formaldehyde and feature peak intensity (1072 ± 2cm-1、1143±2cm-1) linear relationship signal Figure.
Fig. 5 is that various concentration acetaldehyde standard solution enhances p-aminophenyl thiophenol after silver mirror reaction occurs in the embodiment of the present invention Liquid (5 × 10-5Mol/L SERS collection of illustrative plates).
Fig. 6 is the standard concentration of acetaldehyde and feature peak intensity (1072 ± 2cm-1、1143±2cm-1) linear relationship signal Figure.
Fig. 7 is increased after silver mirror reaction occurs for the formaldehyde acetaldehyde mixed standard solution of different relative amounts in the embodiment of the present invention Strong p-aminophenyl thiophenol liquid (5 × 10-5Mol/L SERS collection of illustrative plates).
Fig. 8 is formaldehyde relative amount and feature peak intensity relative value in mixed standard solution in the embodiment of the present invention (I1143cm-1/I1072cm-1) linear relationship schematic diagram.
Fig. 9 is the flow chart of the detection method of the embodiment of the present invention.
Specific embodiment
Technical scheme of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1:μ PAD-SERS technologies detect formaldehyde acetaldehyde hybrid standard liquid
(1) silver ammino solution of the thiophenol containing p-aminophenyl is prepared
The silver nitrate solution of 2mL 0.01moL/L is taken in test tube, adds 100 μ L 0.1moL/L sodium hydrate aqueous solutions, shakes It swings, generates pale yellow precipitate;80 microlitres of weak aqua ammonia is instilled dropwise, until the precipitation initially generated dissolves just, adds 50 μ L 1×10-4Mol/L p-aminophenyl thiophenols prepare the silver ammino solution of the thiophenol containing p-aminophenyl;
(2) the different mixed standard solution of formaldehyde acetaldehyde relative amount is prepared
Prepare six test tubes, be labeled as:1st, 2,3,4,5,6, formaldehyde is taken respectively:0、10、20、30、40、50μL;Acetaldehyde: 100、80、60、40、20、0μL.Prepare the formaldehyde acetaldehyde that content of formaldehyde is respectively 0%, 20%, 40%, 60%, 80%, 100% Mixed standard solution.
(2) structure for formaldehyde and acetaldehyde based on paper microfluidic analysis device μ-PAD
The scraps of paper are cut into rectangularity, both ends are respectively sealed with wax out a border circular areas, and diameter is about 1cm, and one end is as to be measured Area, the other end is as reference region.
(4) silver nano-grain (Ag NPs-ATP) of p-aminophenyl thiophenol modification is prepared by silver mirror reaction
By (1) prepare the silver ammino solution containing ATP be added dropwise respectively in area to be measured and reference region, after area to be measured add in not With the formaldehyde or acetaldehyde solution of concentration, reference region adds in water as control.Occur silver mirror reaction under the conditions of 25 DEG C, after 10min, Area to be measured obtains Ag NPs-ATP, can be used as SERS active-substrate, the thickness of filter membrane is about 6mm.The SEM of Ag NPs-ATP films Figure is as shown in Figure 1.
(5) content of formaldehyde acetaldehyde is detected using the intensity of Portable Raman spectrometer detection p-aminophenyl thiophenol.
Portable surface enhancing Raman spectrometer is detected the film after above-mentioned reaction, excitation wavelength 785nm, during integration Between 30s, obtain the SERS collection of illustrative plates of sample, the spectral contrast with ATP solids is so as to fulfill qualitative and quantitative detection.
For individual formalin, the formaldehyde standard solution (0.01~0.1 μM) of various concentration is prepared, use is portable Raman spectrometer detects its spectral signal (Fig. 2), using 1072 ± 2cm of Raman spectral peaks-1、1143±2cm-1As judgement first The characteristic peak of aldehyde.As the concentration of formaldehyde in solution to be measured is gradually increased (0.01~0.1 μM), 1072 in Raman spectrogram ± 2cm-1、1143±2cm-1Feature peak intensity at two gradually increases (Fig. 3) therewith, selects with 1072 ± 2cm-1、1143±2cm-1 Corresponding peak intensity combination linearity curve (Fig. 4) can the content of PARA FORMALDEHYDE PRILLS(91,95) calculated.
For individual acetaldehyde solution, the acetaldehyde standard solution (0.01~0.1 μM) of various concentration is prepared, use is portable Raman spectrometer detects its spectral signal, using 1072 ± 2cm of Raman spectral peaks-1、1143±2cm-1Spy as judgement acetaldehyde Levy peak.As the concentration of aldehyde in solution to be measured is gradually increased (0.01~0.1 μM), 1072 ± 2cm in Raman spectrogram-1、 1143±2cm-1Feature peak intensity at two gradually increases (Fig. 5) therewith, selects with 1072 ± 2cm-1、1143±2cm-1It is corresponding Peak intensity combination linearity curve (Fig. 6) can calculate the content of acetaldehyde.
For the formaldehyde acetaldehyde mixed solution of different relative amounts, using the formaldehyde for the different relative amounts prepared in (2) Acetaldehyde standard solution (0-100%) detects its spectral signal using Portable Raman spectrometer, using Raman spectral peaks 1072 ± 2cm-1、1143±2cm-1As characteristic peak.As formaldehyde acetaldehyde relative amount is gradually increased (0-100%) in solution to be measured, I in Raman spectrogram1143±2cm-1/I1072±2cm-1Value gradually increase, (Fig. 7) is selected with I1143±2cm-1/I1072±2cm-1Value knot Linear curve (Fig. 8) can the relative amount of PARA FORMALDEHYDE PRILLS(91,95) acetaldehyde calculated.
Embodiment 2:Detect the formaldehyde acetaldehyde in edible wine sample
Fig. 9 schematically illustrates the flow chart of formaldehyde acetaldehyde in the wine of the embodiment of the present invention, and the detection method includes Following steps:
(1) silver ammino solution of the thiophenol containing p-aminophenyl is prepared, step is the same as embodiment 1;
(2) mixed standard solution of formaldehyde acetaldehyde difference relative amount is prepared, step is the same as embodiment 1;
(3) analytical equipment of the formaldehyde acetaldehyde of structure μ-PAD, step is the same as embodiment 1;
(4) silver nano-grain (Ag NPs-ATP) of p-aminophenyl thiophenol modification is prepared by silver mirror reaction, step is the same as real Apply example 1;
(5) μ PAD-SERS detect formaldehyde acetaldehyde in wine.
The wine sample of experiment is the three kinds of wine bought from supermarket.Measure wine in formaldehyde acetaldehyde when, 2mL wine sample directly into μ PAD are operated in row embodiment (1), without other any pretreatments.SERS is carried out by the μ-PAD to formaldehyde adsorption or acetaldehyde Analysis, so as to fulfill the detection of formaldehyde in wine and acetaldehyde, formaldehyde and acetaldehyde are often gas chromatography-mass spectrum with detection method in wine sample Method (SN/T 4675.7-2016), analysis sample is analyzed simultaneously using gas chromatograph-mass spectrometer (GC-MS), as a result such as 1 institute of table Show.
Table 1

Claims (3)

  1. It is 1. a kind of for the method for formaldehyde and acetaldehyde field quick detection in wine, which is characterized in that it uses paper substrate micro-fluidic point Formaldehyde and acetaldehyde in analysis apparatus μ-PAD extraction edible wine samples, using p-aminophenyl thiophenol ATP as probe molecule, utilize silver mirror reaction Enhancing substrates of the silver nano-grain Ag NPs of preparation as Surface enhanced Raman scattering, is established by Portable Raman spectrometer Variation relation between the peak intensity of p-aminophenyl thiophenol and formaldehyde or acetaldehyde, and then realize formaldehyde and acetaldehyde in wine sample to be measured Live fast quantification and qualitative detection.
  2. 2. it according to the method described in claim 1, it is characterized in that, is as follows:
    (1) paper substrate micro-fluidic analytical equipment μ-PAD are made;
    (2) silver ammino solution of the thiophenol containing p-aminophenyl is added dropwise in the area to be measured of paper substrate micro-fluidic analytical equipment μ-PAD, area to be measured The standard solution containing formaldehyde and acetaldehyde separately or together is added dropwise, reacts 10-15min at room temperature, p-aminophenyl is prepared The silver nano-grain Ag NPs-ATP of thiophenol modification, using it as SERS active-substrate, are treated using Portable Raman spectrometer Survey wine sample and carry out Surface enhanced Raman spectroscopy SERS detections, establish the peak intensity of p-aminophenyl thiophenol and formaldehyde or acetaldehyde it Between linear relationship;
    (3) wine sample alternate standard solution to be measured is prepared into SERS active-substrate by step (2), utilizes Portable Raman spectrometer pair Wine sample to be measured carries out Surface enhanced Raman spectroscopy SERS detections, then compares the Raman spectrum of wine sample and standard solution to be measured and linear Relationship, so as to fulfill the live fast quantification and qualitative detection of formaldehyde and acetaldehyde in wine sample to be measured.
  3. 3. according to the method described in claim 2, it is characterized in that, in step (2), the silver ammino solution of the thiophenol containing p-aminophenyl Preparation method is as follows:Take the silver nitrate solution of 2~5mL 0.01moL/L and the oscillation of 100 μ L 0.1moL/L sodium hydrate aqueous solutions Mixing generates pale yellow precipitate;Weak aqua ammonia is instilled dropwise, until the precipitation initially generated dissolves just, adds 50~125 μ L 1×10-4The p-aminophenyl thiophenol of mol/L prepares the silver ammino solution of the thiophenol containing p-aminophenyl.
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CN113324972A (en) * 2021-05-17 2021-08-31 昆明理工大学 Quantitative analysis method for formaldehyde in water environment

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