CN107064109B - A method of detection Benzene in Beverages formic acid - Google Patents

A method of detection Benzene in Beverages formic acid Download PDF

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CN107064109B
CN107064109B CN201710252220.7A CN201710252220A CN107064109B CN 107064109 B CN107064109 B CN 107064109B CN 201710252220 A CN201710252220 A CN 201710252220A CN 107064109 B CN107064109 B CN 107064109B
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extraction
silica gel
substrate
beverages
formic acid
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CN107064109A (en
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王翊如
蔡乐梅
陈曦
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Xiamen University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption

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Abstract

The invention discloses a kind of methods for detecting Benzene in Beverages formic acid, and after being enriched with using silica gel extraction substrate to the benzoic acid in beverage, mating surface enhancing Raman spectroscopy detects it.The present invention is high by film micro-extraction technique extraction efficiency, extraction time is short, the characteristics of can carrying out selective extraction to the object in complex matrices is easy to detect fast with Surface enhanced Raman spectroscopy technology, the advantages of high sensitivity, combines, and provides that a kind of easy to operate, high sensitivity, testing cost be low, measuring method of conveniently Benzene in Beverages formic acid.

Description

A method of detection Benzene in Beverages formic acid
Technical field
The invention belongs to food analysis research fields, and in particular to a method of detection Benzene in Beverages formic acid, especially A kind of method of film micro-extraction mating surface enhancing Raman spectroscopy detection Benzene in Beverages formic acid.
Background technique
Benzoic acid is a kind of acidic preservative, and not dissociating acid has antibacterial activity.Benzoic acid can be used as food and drug is anti- Rotten agent can effectively prevent food and drug rotten, extend the shelf life.Since benzoic acid is in the liquid environment of pH 2.5~4.0 Middle antibacterial activity is most strong, therefore is widely used as the preservative of beverage.Some researches show that the benzoic acid of excess intake may lead Play the symptoms such as diarrhea, abdominal pain and palpitating speed.Excessive benzoic acid can also interfere the intermediate supersession process of human body, including urea to follow Ring, gluconeogenesis, fatty acid metabolism and tricarboxylic acid cycle etc..Main method currently used for detecting benzoic acid content has efficient liquid phase Chromatography (HPLC), gas chromatography (GC), spectrophotometry etc., before these methods have the shortcomings that different or sample Reason process is complex, and perhaps detection needs valuable instrument and equipment or detection to spend longer time.Therefore, it is necessary to Development new method that is a kind of rapidly and efficiently, inexpensive, detecting Benzene in Beverages formic acid in high sensitivity.
Film micro-extraction technique (TFME) is a kind of novel solid phase microextraction (SPME) technology, when with same volume When extraction phase, film micro-extraction technique possesses bigger surface area and more compared with traditional fiber type solid phase micro-extraction technique Thin extract layer thickness, so as to shorten analysis time.In recent years, film micro-extraction be widely used in biochemical analysis, In the various fields such as Analysis on Environment Contamination, Food Safety Analysis.In addition, Surface enhanced Raman spectroscopy (SERS) refers to when analyzed Object Molecular Adsorption is in colloid metallic particles such as silver, golden or copper surface sample, or is adsorbed on the rough surface of these sheet metals, Its raman spectrum strength can be improved 103~106A kind of spectral technique again.Compared to traditional analysis detection technique, surface enhanced is drawn Noninvasive detection may be implemented in graceful spectrum, is suitable for a variety of systems such as aqueous solution, and almost prepares without sample, measures Journey is convenient and efficient, these advantages make SERS technology as research hotspot in recent years.But there is not a kind of micro- extraction of film also at present The method for taking mating surface enhancing Raman spectroscopy detection benzoic acid.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of side for detecting Benzene in Beverages formic acid Film micro-extraction technique and Surface enhanced Raman spectroscopy technology are combined by method, and the selectivity analysis of para Toluic Acid both may be implemented, Again can para Toluic Acid be used for quickly detecting, to improve sensitivity for analysis and shorten detection time.
The technical solution adopted by the present invention to solve the technical problems is:
A method of detection Benzene in Beverages formic acid, comprising:
1) silica gel extraction substrate is prepared:
Hydroxylating processing 1-1) is carried out to glass sheet substrate: 0.8~1.2cm × 0.8~1.2cm sheet glass is successively existed Ultrapure water, ethyl alcohol are respectively cleaned by ultrasonic 8~12min in acetone, are dried with nitrogen；Separately by the concentrated sulfuric acid and hydrogen peroxide according to volume ratio 6~ 8:2~4 is mixed, cooling；The sheet glass being dried with nitrogen is added into the concentrated sulfuric acid and dioxygen water mixed liquid, 85~95 DEG C of water After 0.5~1.5h of bath heating, sheet glass is taken out, ultrapure water is dried with nitrogen；
1-2) be added sodium carboxymethylcellulose into 55~65 DEG C of ultrapure water, stirring and dissolving, obtain concentration be 0.3~ 0.5% carboxymethylcellulose sodium solution；
1-3) carboxymethylcellulose sodium solution for obtaining step 1-2) and thin-layer chromatography silica gel according to 2~4mL:0.5~ The formula rate of 1.5g mixes, and stirs evenly, obtains paste；
The obtained paste of step 1-3) 1-4) is coated in rapidly step 1-1) on obtained sheet glass, continuous vibration glass Piece makes paste thereon be evenly distributed；
1-5) sheet glass for being coated with paste for obtaining step 1-4) places naturally dry in the horizontal plane, then exists 100~110 DEG C of dry 20~40min extract substrate to get the silica gel, and it is in macroscopic plane form, glass which, which extracts substrate, For the layer of silica gel coated in glass piece substrate with a thickness of 100~150 μm, the silica gel material in layer of silica gel is in the coarse unformed shape of multiple hole State；
Silica gel material is that one kind has open porous structure, strong adsorption, all has absorption property to gas chromatography matter Fiber material, and silica gel chemical inertness is very strong, solvent resistant, it is not easy to chemical change occur.As film micro-extraction Material, it is not only low in cost, it more can achieve the good concentration effect of benzoic acid.
In addition, the silica gel extraction substrate of macroscopic plane form can provide bigger specific surface area, and low in cost, system It is standby quick；The substrate of glass increased hydrophilicity handled through hydroxylating, makes silica gel be easier to spread out, is conducive to the uniform of silica gel material Distribution has better detection effect；The silica gel extraction substrate of macroscopic plane form is conducive to spray or be added dropwise to be suitable for surface Enhance the enhancing substrate of Raman spectrum analysis, and be convenient for the irradiation of raman laser, so as to be used for Surface enhanced Raman spectroscopy Analysis.
2) object benzoic acid in film micro-extraction enrichment sample to be tested: sample to be tested is not necessarily to any pretreatment, will be to be measured Sample moves into film micro-extraction device, the extraction substrate of silica gel made from step 1) is immersed in sample to be tested, in room temperature, 800 Film micro-extraction is carried out under~1500rpm stirring rate, after extracting 15~25min, is taken out silica gel and is extracted substrate, volatilize moisture；
3) object benzoic acid in Surface enhanced Raman spectroscopy technology detection sample to be tested: the AuNPs that 4~12 μ L are concentrated It is added dropwise and extracts substrate surface in the silica gel that step 2) obtains, detected later with Raman instrument.
In one embodiment: in the step 2), film micro-extraction device includes extraction bracket and body；The extraction bracket packet Include bottle cap, gasket and support frame；The bottle cap is adapted to attaching with the body, and the gasket is set in the bottle cap, the branch Support is located in body, and support frame top and gasket are affixed, and support frame lower part is equipped with for placing the silica gel extraction substrate U-shaped platform.
In one embodiment: the volume of the body is 10~50mL；
In one embodiment: support frame as described above length is 5~7cm；
In one embodiment: the width of support frame as described above is 0.5~1.0cm.
In one embodiment: support frame as described above is made of aluminium flake.
In one embodiment: in the step 3), concentration AuNPs's the preparation method comprises the following steps: by 4.5mL be commercialized gold nano (Xiamen Pu Shi nanosecond science and technology Co., Ltd, model CP-1, gold nano grain concentration are about 0.3mmol/L to solution stoste, average Partial size is 55nm.) under the conditions of 3000~5000rpm be centrifuged 10~20min after discard supernatant liquid to be concentrated into 0.1mL.
The technical program compared with the background art, it has the following advantages:
Film micro-extraction technique in conjunction with Surface enhanced Raman spectroscopy technology, is utilized film micro-extraction technique point by the present invention It is detected from the benzoic acid in enriched sample, then using Surface enhanced Raman spectroscopy technology；The benzene ring structure of benzoic acid molecule With very strong Raman signal, the interference of other molecules can be excluded to a certain extent.This method is low in cost, easy to operate, High sensitivity detects the rapidly and efficiently measurement of benzoic acid suitable for the various samples such as beverage.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 (a) is the SEM figure that the silica gel prepared in the embodiment of the present invention extracts silica gel material in layer of silica gel on substrate；Fig. 1 (b) the section SEM figure of substrate is extracted for silica gel.
Fig. 2 is that different sample point SERS spectra reproducibility results are shown on same silica gel extraction substrate in experimental example 2 of the present invention It is intended to, abscissa is Raman shift (cm in figure-1), ordinate is intensity (a.u.).
Fig. 3 is the reproducibility result signal that different silica gel extract substrate extraction with concentration benzoic acid in experimental example 2 of the present invention Scheme, ordinate is peak intensity (a.u.) in figure.
Fig. 4 is the Raman for measuring various concentration benzoic acid solution in experimental example 3 of the present invention with TFME-SERS method of the invention Spectrogram and its range of linearity, Fig. 4 (a) coordinate are respectively Raman shift (cm-1), concentration (μ g/mL), intensity (a.u.)；Fig. 4 (b) abscissa is concentration (μ g/mL) in, and ordinate is peak intensity (a.u.).
Fig. 5 is to measure concentration of benzoic acid in different drink samples with TFME-SERS method of the invention in experimental example 4 of the present invention Raman spectrogram: sample 1 (a), (b) sample 2, (c) sample 3, (d) sample 4, (e) sample 5 and (f) benzoic acid standard is molten Liquid (500 μ g mL-1), abscissa is Raman shift (cm in figure-1), ordinate is intensity (a.u.).
Fig. 6 is the structure and assembling process schematic diagram of film micro-extraction device of the invention, and wherein a is extraction bracket, and b is Body, 1 is support frame top, and 2 be gasket, and 3 be support frame, and 4 be support frame lower part, and 5 be bottle cap.
Specific embodiment
The contents of the present invention are illustrated below by embodiment:
Embodiment
A kind of method (TFME-SERS method) detecting Benzene in Beverages formic acid, comprising:
1) silica gel extraction substrate is prepared:
Hydroxylating processing 1-1) is carried out to glass sheet substrate: the sheet glass of 1.0cm × 1.0cm size is successively existed Ultrapure water, ethyl alcohol are respectively cleaned by ultrasonic 10min in acetone, are dried with nitrogen；The 35mL concentrated sulfuric acid is separately added into beaker, while stirring The hydrogen peroxide of 15mL is added thereto, after mixed liquor is cooling, the sheet glass being dried with nitrogen after cleaning is added to the concentrated sulfuric acid In dioxygen water mixed liquid, after 90 DEG C of heating water bath 1h, sheet glass is taken out, ultrapure water is dried with nitrogen；
0.12g sodium carboxymethylcellulose 1-2) is added into 60 DEG C of 30mL ultrapure water, stirring and dissolving, obtaining concentration is 0.4% carboxymethylcellulose sodium solution；
1-3) the carboxymethylcellulose sodium solution 30mL that step 1-2) is obtained is poured into mortar, 10g thin layer is then added (G type or GF254 type, the thin-layer chromatography silica gel selected in the present embodiment is purchased from Aladdin reagent Co., Ltd, G for chromatography silica gel Type, SKU T116946), it stirs evenly, obtains paste；
The obtained paste of step 1-3) 1-4) is coated in rapidly step 1-1 with glass bar) on obtained sheet glass, constantly Vibration sheet glass makes paste thereon be evenly distributed；
1-5) sheet glass for being coated with paste for obtaining step 1-4) places naturally dry in the horizontal plane, then exists Dry 30min, takes out and extracts substrate to get the silica gel, be put into drier in 105 DEG C of baking ovens, spare；The silica gel extracts base Plate is in macroscopic plane form, and the layer of silica gel coated in glass sheet substrate is with a thickness of 130 μm, and the silica gel material in layer of silica gel is in porous The coarse unformed state in hole；
2) sample to be tested object benzoic acid in film micro-extraction (TFME) enrichment sample to be tested: is moved into film micro-extraction In device, the film micro-extraction device is as shown in fig. 6, include extraction bracket a and body b；Extraction bracket a include bottle cap 5, Gasket 2 and support frame 3；The bottle cap 5 is adapted to attaching with the body b, and the gasket 2 is set in the bottle cap 5, the support Frame 3 is located in body b, and support frame top 1 and gasket 2 are affixed, and support frame lower part 4 is equipped with for placing the silica gel extraction base The U-shaped platform of plate.
The bottle cap 5 of the film micro-extraction device and body b can be restructured using existing serum bottle cap and body and At support frame 3 is made of the aluminium flake of 5.5~6.5cm of length, 0.6~0.8cm of width.The assembling of film micro-extraction device Journey is as shown in Fig. 6: as needed, selecting the serum bottle of 10~30mL of volume, the gasket 2 in bottle cap 5 is taken out and at middle part An osculum is opened, aluminium flake upper end is passed through into osculum and exceeds about 0.5cm, part fold is will exceed and is fixed on 2 upper surface of gasket, aluminium Piece lower end takes 1cm flat-folded perpendicular to aluminium flake, and end takes 0.2~0.3cm vertically to turn up again, makes lower part that U be presented Type forms the U-shaped platform, for placing silica gel extraction substrate, prevents from falling；Then gasket 2 is put back in bottle cap 5, so Form extraction bracket a.
Sample to be tested 10mL is added to the body b of film micro-extraction device, silica gel extraction substrate is placed on extraction bracket a U type platform on, then extraction bracket a by bottle cap 5 and body b is threadedly engaged attaching, 3 lower part of support frame and silica gel extract Substrate immerses under sample to be tested liquid level, and is located at silica gel extraction substrate in the middle part of sample to be tested liquid；Then stirred in room temperature, magneton It mixes and carries out film micro-extraction under conditions of rate 1000rpm, after extracting 20min, take out extraction bracket a, remove silica gel extraction base Plate simultaneously volatilizes moisture, remains to detect in next step；
3) object benzoic acid in Surface enhanced Raman spectroscopy technology (SERS) detection sample to be tested: 5~10 μ L are concentrated AuNPs the silica gel obtained in step 2) be added dropwise extract substrate surface, detected later with Raman instrument.The concentration After AuNPs's the preparation method comprises the following steps: be centrifuged 15min under the conditions of 4000r/min for the 4.5mL gold nano solution stoste being commercialized, Liquid is discarded supernatant, to be concentrated into 0.1mL.
Above-described embodiment can realize the effect of following experimental examples:
Experimental example 1
This experimental example characterizes the extraction substrate of silica gel obtained in embodiment.Fig. 1 a is that silica gel extracts silicon on substrate The scanning electron microscope (SEM) photograph of silica gel thin film fiber material in glue-line shows in figure the silica gel material surface microscopic in coarse unformed shape State has compared with multiple hole, this makes the coating have more adsorption site and biggish adsorption area.As shown in Figure 1 b, from Silica gel extracts the section SEM figure of substrate it is found that the thickness of silica gel extraction coating is about 130 μm, and relatively thin coating layer thickness is advantageous In the quick progress of mass transport process, and biggish extraction area ensure that biggish adsorption capacity, facilitate analysis method spirit The raising of sensitivity.
Experimental example 2
This experimental example examines the reproducibility of detection method in embodiment, to the different sample points of same silica gel extraction substrate The reproducibility of SERS signal and different silica gel extraction substrates investigate the reproducibility of same analyte signal.Firstly, real The standard solution using the benzoic acid of 500 μ g/mL is tested as extract liquor, monolithic silica gel extraction substrate is chosen and carries out TFME process, 10 region points then, which are randomly selected, in the range of extracting piece sprinkling gold size nanoparticle acquires its SERS signal, acquired results As shown in Figure 2.It can be seen that the SERS signal of income analysis object benzoic acid is fairly obvious in silica gel extraction substrate different zones, and Consistency with higher.
Secondly, experiment randomly selects 5 different silica gel extraction substrates, and it is molten to be applied to same concentration benzoic acid standard During the reproducibility of liquid TFME-SERS detection is investigated, signal acquisition 5 times of each silica gel extraction substrate, gained benzoic acid characteristic peak Strength difference it is as shown in Figure 3.The SERS signal RSD of different silica gel extraction substrate extraction benzoic acid detections is 10.2%, display Higher reproduction degree out.
Experimental example 3
It is right respectively with this method that this experimental example has investigated the range of linearity of detection method and detection limit, experiment in embodiment The benzoic acid standard solution of 25 μ of μ g/mL~500 g/mL is determined.When measurement, respectively by 25 μ of μ g/mL~500 of 10mL The benzoic acid standard solution of g/mL moves into 10mL serum bottle, and silica gel extraction substrate is placed in film micro-extraction device and is immersed In sample.Solution is in stirring in extraction process, and magneton stirring rate is 1000rpm, extraction time 20min, extraction Temperature is room temperature, and after the completion of extraction process, silica gel extraction substrate is removed from film micro-extraction device.Substrate is extracted to silica gel After surface moisture volatilization, the AuNPs after the concentration of 10 μ L gold size solution is added dropwise and extracts substrate surface in silica gel, is increased later with surface Strong Raman spectrum is detected.All measurement samples are triplicate, and Surface enhanced Raman spectroscopy data acquire 3 times, gained Data are the average value of measurement result.
Gained SERS spectrogram and linear relationship can be seen that the drop with concentration of benzoic acid as shown in figures 4 a and 4b, from Fig. 4 a Low, the SERS spectrogram intensity of benzoic acid also accordingly reduces, until feature spectrogram is still high-visible when 25 μ g/mL of low concentration, Illustrate that the sensitivity of this method is higher.Fig. 4 b is with the strongest characteristic peak 994cm of benzoic acid-1Opposite peak intensity be ordinate, benzene first Acid concentration is abscissa to draw standard curve, and linearly dependent coefficient reaches 0.995, is shown preferable linear.It is computed, This method detection is limited to 3.6 μ g/mL (S/N=3), complies fully with the testing requirements of Benzene in Beverages formic acid.
Experimental example 4
This experimental example has investigated the reliability of detection method in embodiment, and experiment is using high in GB/T 5009.29-2003 Effect liquid phase chromatogram method is determined the content of benzoic acid in 8 kinds of different commercial beverage, result such as table as contrast method Shown in 1 and Fig. 5.It can be seen that from result, the measurement result of two methods is almost the same, illustrates that the new method established is with higher Reliability.And extractive analysis while TFME-SERS method can realize multiple samples, to greatly shorten analysis time.By Fig. 5 It is found that actual sample and the Raman spectrogram spectral peak that benzoic acid standard solution is obtained by TFME-SERS are more consistent, and real Do not occur the biggish miscellaneous peak of intensity in the spectrogram of border sample, illustrates that this method can substantially reduce the background interference of detection, one Determine to realize selective enumeration method in degree.
1 TFME-SERS of table and national standard method measure Benzene in Beverages formic acid Comparative result
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.

Claims (7)

1. a kind of method for detecting Benzene in Beverages formic acid, it is characterised in that: include:
1) silica gel extraction substrate is prepared:
0.8~1.2cm × 0.8~1.2cm sheet glass 1-1) is successively respectively cleaned by ultrasonic in ultrapure water, ethyl alcohol, acetone to 8~ 12min is dried with nitrogen；Separately the concentrated sulfuric acid and hydrogen peroxide are mixed according to 6~8:2 of volume ratio~4, it is cooling；The glass that will be dried with nitrogen Glass piece is added into the concentrated sulfuric acid and dioxygen water mixed liquid, after 85~95 DEG C of 0.5~1.5h of heating water bath, takes out sheet glass, surpasses Pure water rinsing is dried with nitrogen；
Sodium carboxymethylcellulose 1-2) is added into 55~65 DEG C of ultrapure water, stirring and dissolving, obtaining concentration is 0.3~0.5% Carboxymethylcellulose sodium solution；
1-3) carboxymethylcellulose sodium solution for obtaining step 1-2) and thin-layer chromatography silica gel are according to 2~4mL:0.5~1.5g Formula rate mixing, stir evenly, obtain paste；
The obtained paste of step 1-3) 1-4) is coated in rapidly step 1-1) on obtained sheet glass, constantly vibrating sheet glass makes Paste thereon is evenly distributed；
1-5) sheet glass for being coated with paste for obtaining step 1-4) places naturally dry in the horizontal plane, then 100 ~110 DEG C of dry 20~40min extract substrate to get the silica gel, and it is in macroscopic plane form, sheet glass which, which extracts substrate, The layer of silica gel coated in substrate is with a thickness of 100~150 μm；
2) object benzoic acid in film micro-extraction enrichment sample to be tested: sample to be tested is moved into film micro-extraction device, will Silica gel made from step 1) extracts substrate and immerses in sample to be tested, carries out film under room temperature, 800~1500rpm stirring rate Micro-extraction after extracting 15~25min, takes out silica gel and extracts substrate, volatilize moisture；
3) object benzoic acid in Surface enhanced Raman spectroscopy technology detection sample to be tested: the AuNPs of 4~12 μ L concentration is added dropwise Substrate surface is extracted in the silica gel that step 2) obtains, is detected later with Raman instrument.
2. the method for detection Benzene in Beverages formic acid according to claim 1, it is characterised in that: in the step 2), film Micro-extraction device includes extraction bracket and body；The extraction bracket includes bottle cap, gasket and support frame；The bottle cap and the bottle Body is adapted to attaching, and the gasket is set in the bottle cap, and support frame as described above is located in body, and support frame top and gasket are solid It connects, support frame lower part is equipped with the U-shaped platform for placing the silica gel extraction substrate.
3. the method for detection Benzene in Beverages formic acid according to claim 2, it is characterised in that: the volume of the body is 10 ~50mL.
4. the method for detection Benzene in Beverages formic acid according to claim 2, it is characterised in that: support frame as described above length is 5 ~7cm.
5. the method for detection Benzene in Beverages formic acid according to claim 2, it is characterised in that: the width of support frame as described above is 0.5~1.0cm.
6. the method for detection Benzene in Beverages formic acid according to claim 2, it is characterised in that: support frame as described above is aluminium flake system At.
7. the method for detection Benzene in Beverages formic acid according to claim 1, it is characterised in that: in the step 3), concentration AuNPs's the preparation method comprises the following steps: 4.5mL gold nano solution stoste is centrifuged 10~20min under the conditions of 3000~5000rpm after Liquid is discarded supernatant to be concentrated into 0.1mL.
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