CN109482163A - Amination Metaporous silicon dioxide material, preparation method and application and regeneration method in synthetic dyestuff assay and purification - Google Patents
Amination Metaporous silicon dioxide material, preparation method and application and regeneration method in synthetic dyestuff assay and purification Download PDFInfo
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- CN109482163A CN109482163A CN201811486896.3A CN201811486896A CN109482163A CN 109482163 A CN109482163 A CN 109482163A CN 201811486896 A CN201811486896 A CN 201811486896A CN 109482163 A CN109482163 A CN 109482163A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
Abstract
The present invention provides a kind of amination Metaporous silicon dioxide material, preparation method and application and regeneration method in synthetic dyestuff assay and purification, it disperses Metaporous silicon dioxide material in appropriate solvent, then it is proportionally added into 3- aminopropyl trimethoxy siloxane, heating reflux reaction is finally carried out, is post-processed after reaction up to amination Metaporous silicon dioxide material.Since its surface grafting has amino, adsorption capacity significantly increases amination Metaporous silicon dioxide material of the present invention, can reach complete absorption to azo pigment, effectively improve the accuracy of food synthetic pigment assay.
Description
Technical field
The invention belongs to the technical fields of food synthetic pigment detection, and in particular to a kind of amination mesoporous silicon oxide material
Material, preparation method and application and regeneration method in synthetic dyestuff assay and purification.
Background technique
The use of edible pigment is very universal in modern food processing.Edible pigment includes natural pigment and synthetic dyestuff,
Natural pigment the disadvantages of there are at high cost, tinting strength, tinting power is poor, stability is poor, and synthetic dyestuff is bright in luster, cheap, steady because of its
The advantages that qualitative good, by the favor of food production producer, therefore, synthetic dyestuff is widely used in the food industry.
However, partially synthetic pigment, especially azo synthetic dyestuff, can be converted to derivative harmful to health in human body.Also,
More and more researches show that the synthetic dyestuff of most of types will increase Human Health Risk, such as allergy, asthma, DNA damage
Wound, hyperactivity hyperkinesia or even carcinogenic.Therefore, food industry must be strictly controlled the use of synthetic dyestuff, with ensure food safety and
Consumer health.And some bad manufacturers are driven by interests, use to excess over range synthetic dyestuff, even with disabling
In food and the pigment and dyestuff of harmful human body, the dyeing steamed bun event occurred before, which further demonstrates, to be established one kind and has
Effect, convenient and fast food synthetic pigment measuring method are extremely important.
Nowadays, high performance liquid chromatography (HPLC) because its high sensitivity, selectivity it is good due to be widely used in secondary colour in food
The measurement of cellulose content.However, since sample has complicated matrix effect, pigment content is very low in direct continuous mode,
Can not be accurate so will lead to a large amount of data, therefore, carried out before the measurement of synthetic dyestuff in food sample pre-treatments be to
Close important, and dispersive solid-phase extraction is a kind of simple and common sample-pretreating method, in dispersive solid-phase extraction process
In, the selection of adsorbent is most critical, first have to reach complete absorption, and most of nano material such as carbon nanometer
Pipe, TiO2Nanometer rods, metal organic frame MOFs and Al2O3Deng the complete absorption that cannot all reach to pigment, this is just from the root
Limit the accuracy of food colour assay.
Summary of the invention
The present invention exists for adsorbent used in food colour continuous mode in the prior art adsorbs incomplete ask
Topic provides a kind of amination Metaporous silicon dioxide material, preparation method and in synthetic dyestuff assay and purification
Using and regeneration method, since its surface grafting has amino, adsorption capacity significantly increases the amination Metaporous silicon dioxide material
By force, complete absorption can be reached to azo pigment, effectively improves the accuracy of food synthetic pigment assay.
The present invention adopts the following technical scheme:
A kind of preparation method of amination Metaporous silicon dioxide material is prepared using the method in CN107583599A first
Monodisperse mesoporous silica material disperses gained monodisperse mesoporous silica material in appropriate solvent, then by than
3- aminopropyl trimethoxy siloxane is added in example, finally carries out heating reflux reaction, is post-processed after reaction up to amination
Metaporous silicon dioxide material；
Wherein, the molar ratio of the monodisperse mesoporous silica material and 3- aminopropyl trimethoxy siloxane that are added is 3 ~ 6:
1。
Above-mentioned preparation method specifically includes the following steps:
1) monodisperse mesoporous silica material is prepared using the method in CN107583599A；
2) monodisperse mesoporous silica material obtained by step 1) is taken to be added in appropriate dehydrated alcohol in proportion, and ultrasonic disperse
Obtain reaction solution；
3) take 3- aminopropyl trimethoxy siloxane in proportion and be added dropwise in the reaction solution of step 2), then 90 ~
130 °C of lower heating reflux reaction 10-14 h；The purpose of reflux is that, by experimental verification, more have under high-temperature condition for upper amino
Help upper amino；
4) solution after reacting is cooled to room temperature, and is collected by centrifugation solid precipitating, and with second alcohol and water after alternately washing is multiple, vacuum
Drying is to get amination Metaporous silicon dioxide material.
The amination Metaporous silicon dioxide material that the preparation method is prepared.
Amination Metaporous silicon dioxide material the answering in synthetic dyestuff assay and synthetic dyestuff purification enrichment
With the amination Metaporous silicon dioxide material is used as adsorbent.
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay, comprising the following steps:
1) it draws standard curve: the standard substance of a variety of synthetic dyestuffs being taken to be configured to a series of standard solution of concentration gradients respectively
And HPLC detection is carried out, regression analysis is then made to its concentration with peak area corresponding to the standard solution, is respectively obtained each
The concentration of standard solution of pigment and the standard curve of its peak area；
2) HPLC of synthetic dyestuff content is detected in sample to be tested: firstly, sample to be tested progress pre-treatment is obtained initial sample
The amination Metaporous silicon dioxide material, amination Metaporous silicon dioxide material is added in solution in the initial sample solution
In initial sample solution after the completion of evenly dispersed and absorption, the amination meso-porous titanium dioxide for being adsorbed with synthetic dyestuff is collected by centrifugation
Silicon materials；Then, it disperses the amination Metaporous silicon dioxide material that gained is adsorbed with synthetic dyestuff in desorption solvent, can weigh
It is multiple that repeatedly thus synthetic dyestuff, which desorbs to be scattered in desorption solvent, obtains stripping workshop, it is dry to stripping workshop later at
Reason obtains synthetic dyestuff sample；Gained synthetic dyestuff sample preparation is finally taken to obtain solution to be measured, the volume of solution to be measured can
Meet HPIC detection volume, HPLC is carried out to the solution to be measured and detects to obtain peak area, compares the standard in step 1)
Curve further calculates to obtain synthetic dyestuff content in sample to be tested.
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay, the synthetic dyestuff are
Azo synthetic dyestuff.
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay, the azo secondary colour
Element includes sunset yellow, lemon yellow, amaranth, lures red and orange beta-naphthol.
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay, the chromatography of HPLC detection
Condition are as follows: chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm, 3.5 μm；Mobile phase: (A) 0.02M
Ammonium acetate；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；6.5-10 min, 32% B；10-14
Min, 32%-15% B；Flow velocity: 0.5mL/min；The red Detection wavelength of sunset yellow, lemon yellow, amaranth, temptation is 254nm, orange
The Detection wavelength of Huang II is 485nm.
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay and synthetic dyestuff purification, institute
Stating amination Metaporous silicon dioxide material can regenerate by the following method after adsorbing use: the amination after collecting absorption use
Metaporous silicon dioxide material is scattered in desorption solvent, and ultrasonic treatment is centrifugally separating to obtain the mesoporous dioxy of amination later
Silicon nitride material after being so repeated as many times, finally obtained amination Metaporous silicon dioxide material is dried, that is, is completed again
It is raw.
Beneficial effects of the present invention are as follows:
In the nano material used as adsorbent, mesoporous silicon oxide is answered because synthesis process is simple and product is simple and easy to get
With extensive.And mesoporous silicon oxide large specific surface area itself, even aperture distribution, this is also the basic category as adsorbent material
Property.Contain great amount of hydroxy group in view of meso-porous titanium dioxide silicon face, it is easy to be modified in its surface grafting organic group, amination
Amination mesoporous silica nano-particle is obtained after processing, since its surface grafting has amino, increases its positive surface charge,
Adsorption capacity significantly increases, therefore has good adsorption effect, through experimental test, the mesoporous dioxy of amination to azo pigment
SiClx is enriched with a variety of azo pigments in use, can adsorb simultaneously as adsorbent, and it is only necessary to a few minutes with regard to adsorbable
Completely, enrichment times are up to 120 times or more (enrichment times calculations herein are as follows: the secondary colour that will be obtained after absorption enrichment
The solution to be measured that element dissolution obtains carries out the peak area that HPLC is detected and carries out divided by the initial sample solution before absorption enrichment
HPLC detects resulting peak area to get enrichment times are arrived), other adsorbents are compared, are examined being applied to azo pigment content
When survey field, the accuracy of testing result fundamentally ensure that, improve detection efficiency；And it is being applied to the net of azo pigment
When change field, time cost is saved significantly, and can reach preferable clean-up effect.In addition, the present invention is also to mesoporous dioxy
Absorption property before and after SiClx amination has carried out comparison (see figure 3), the result is that unexpected, the peak area of the two is (quite
In enrichment times) difference decades of times, this also sufficiently proves that ammoxidation of the invention is determined to what raising absorption property was played
Qualitative effect.
Amination mesoporous silicon oxide adsorption time of the present invention is short, and completely, enrichment purification is high-efficient, linear model for absorption
Width is enclosed, is 0.45-1000ng/mL, detection limit is down to 0.1 ng/mL, and amination mesoporous silicon oxide itself has well
Biocompatibility, secondary pollution not will cause to environment.This method has the advantages that be simple and efficient, and the mesoporous dioxy of amination
The preparation process of SiClx is simple, convenient for large-scale production.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of amination Metaporous silicon dioxide material obtained by embodiment 1；
Fig. 2 is the infrared chromatogram of 1 intermediary hole silica of embodiment and amination mesoporous silicon oxide；
Fig. 3 is the comparison diagram of mesoporous silicon oxide and amination mesoporous silicon oxide to synthetic dyestuff absorption property；
Fig. 4 is the standard chromatogram of 5 kinds of synthetic dyestuffs in embodiment 2 and 3, in figure, 1: and lemon yellow, 2: amaranth, 3: sunset yellow,
4: temptation is red, and 5: orange beta-naphthol；
Fig. 5 is the canonical plotting of sunset yellow in embodiment 2 and 3；
Fig. 6 is the canonical plotting of lemon yellow in embodiment 2 and 3；
Fig. 7 is to lure red canonical plotting in embodiment 2 and 3；
Fig. 8 is the canonical plotting of amaranth in embodiment 2 and 3；
Fig. 9 is the canonical plotting of orange beta-naphthol in embodiment 2 and 3；
Figure 10 is the liquid chromatogram of synthetic dyestuff in primverose in embodiment 2, in figure, a: unused amination mesoporous silicon oxide
Adsorb the liquid chromatogram of the original corn sugar juice of enrichment；B: it is waited for the primverose after the absorption of amination mesoporous silicon oxide
Survey the liquid chromatogram of solution；C: the mixed standard solution of 5 kinds of pigments of 200 ng/mL is first carried out to original corn sugar juice
Mark-on, with the liquid chromatogram after the absorption enrichment of amination mesoporous silicon oxide after mark-on；D: first standard solution is carried out
The mark-on of the mixed standard solution of 5 kinds of pigments of 200 ng/mL, with after the absorption enrichment of amination mesoporous silicon oxide after mark-on
Liquid chromatogram；1: lemon yellow, 2: amaranth, 3: sunset yellow, 4: temptation is red, and 5: orange beta-naphthol；
Figure 11 is the liquid chromatogram of synthetic dyestuff in children's edible biscuits in embodiment 3, in figure, a: unused amination mesoporous two
The liquid chromatogram of initial children's biscuit solution of silica absorption enrichment；B: after the absorption of amination mesoporous silicon oxide
The liquid chromatogram of children's biscuit solution to be measured；C: 5 kinds of pigments of 200 ng/mL are first carried out to initial children's biscuit solution
The mark-on of mixed standard solution, with the liquid chromatogram after the absorption enrichment of amination mesoporous silicon oxide after mark-on；D: first to mark
Quasi- solution carries out the mark-on of the mixed standard solution of 5 kinds of pigments of 200 ng/mL, is inhaled after mark-on with amination mesoporous silicon oxide
Liquid chromatogram after attached enrichment；1: lemon yellow, 2: amaranth, 3: sunset yellow, 4: temptation is red, and 5: orange beta-naphthol.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, with reference to the accompanying drawing and specifically
Embodiment is further illustrated technical solution of the present invention.
Embodiment 1
The preparation process of amination Metaporous silicon dioxide material is as follows:
1) it synthesizes to obtain monodisperse mesoporous silica material using the method for CN107583599A；
2) dehydrated alcohol that the resulting monodisperse mesoporous silica material of 1.5-5 g step 1) is added to 100-150 mL is weighed
In, and ultrasonic disperse 10-30 min;
3) the 3- aminopropyl trimethoxy siloxane of 1.4-3.5 mL is added dropwise in the reaction solution of step 2), and should
Reaction solution heating reflux reaction 10-14 h under the conditions of 110 °C;
4) solution after reacting step 3) is cooled to room temperature, solid material is collected by centrifugation, and alternately washing is more with second alcohol and water
After secondary, it is put into vacuum oven and dries to get amination Metaporous silicon dioxide material, it is spare.
Amination Metaporous silicon dioxide material is subjected to TEM test, it can be seen that gained amination mesoporous silicon oxide material
Material is form of spherical particles, and particle size is relatively uniform, while carrying out infrared test to amination Metaporous silicon dioxide material, red
It can be seen that 1456cm in outer spectrogram-1There is a characteristic peak at place, this feature peak be exactly be-NH2The stretching vibration peak of middle N-H, explanation
Mesoporous silicon oxide has succeeded amination.
For the absorption property for verifying amination silica, the present invention has done pair the performance before and after silica amination
Than test, that is, sunset yellow, lemon yellow, amaranth, the red standard items with 5 kinds of pigments of orange beta-naphthol of temptation is taken to prepare two groups of identical marks
Quasi- solution, and the silica before and after being separately added into amination in two groups of standard solution, carry out HPLC test, wherein HPLC
The chromatographic condition of measurement is as follows:
Chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm, 3.5 μm；Mobile phase: (A) 0.02M second
Sour ammonium；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；6.5-10 min, 32% B；10-14
Min, 32%-15% B；Flow velocity: 0.5mL/min, the red Detection wavelength of sunset yellow, lemon yellow, amaranth, temptation is 254nm, orange
The Detection wavelength of Huang II is 485nm, column temperature: 25 °C；Sample volume: 5 μ L.
Test results are shown in figure 3, it can be seen that and the peak area (being equivalent to enrichment times) of the two differs decades of times, this
Also the decisive role that ammoxidation of the invention plays raising absorption property is sufficiently proved.
Embodiment 2
Application of the amination Metaporous silicon dioxide material in primverose synthetic dyestuff assay, comprising the following steps:
The first step draws standard curve
Accurately weigh the following synthetic dyestuff of 5mg respectively: sunset yellow, amaranth, lures red and orange beta-naphthol at lemon yellow, is placed in dry
In dry vial, the ultrapure water that 5mL is added is configured to the standard items mother liquor stock solution of concentration 1mg/mL, and sealing is placed on ice
It is stored for future use in case.
The mother liquor stock solution of above-mentioned synthetic dyestuff is diluted respectively, is configured to 1.0 μ g/mL, 0.5 μ g/mL, 0.2 μ
G/mL, 0.1 μ g/mL, 0.05 μ g/mL, 0.025 μ g/mL, 0.01 μ g/mL, a series of 0.005 concentration of μ g/mL standard
Working solution carries out HPLC measurement, obtains the peak area of various criterion solution and and corresponding concentration fit standard curve；Such as Fig. 4
For the standard chromatogram of 5 kinds of synthetic dyestuffs；Fig. 5 to 9 is respectively sunset yellow, lemon yellow, the mark for luring red, amaranth, orange beta-naphthol
Directrix curve figure.
Wherein, the chromatographic condition of HPLC measurement is as follows:
Chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm, 3.5 μm；Mobile phase: (A) 0.02M second
Sour ammonium；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；6.5-10 min, 32% B；10-14
Min, 32%-15% B；Flow velocity: 0.5mL/min, the red Detection wavelength of sunset yellow, lemon yellow, amaranth, temptation is 254nm, orange
The Detection wavelength of Huang II is 485nm, column temperature: 25 °C；Sample volume: 5 μ L.
Second step, the measurement of synthetic dyestuff content in primverose
The primverose sample for accurately weighing 1.0g, is put into the centrifuge tube of 50mL after smashing to pieces, and 20mL ultrapure water is added wherein
It is dissolved, for quick, abundant dissolution, can be heated to 60 °C and stir several minutes, after dissolution, be cooled to room temperature, centrifugation is gone
Except undissolved precipitating, supernatant is crossed to 0.45 μm of filter membrane later, it is molten as original corn sugar that 10mL(is taken out from filtrate
Liquid) enrichment absorption is carried out, adsorption method is as follows: the amination mesoporous silicon oxide adsorbent of 5-15 mg is added in filtrate
Ultrasonic 10-15 min carries out enrichment absorption, and centrifugal treating outwells supernatant, and collecting solid precipitating, (solid precipitating is to be adsorbed with
The amination Metaporous silicon dioxide material of synthetic dyestuff), by the desorption solvent of 20mL, (desorption solvent is third that volume ratio is 8:2
The mixed solution of ketone and the B-R buffer solution of pH=11) it is added to ultrasound desorption in above-mentioned solid precipitating, ultrasound desorption can be multiple
Supernatant is collected by centrifugation later, is dried up in mild nitrogen atmosphere, and with 500 μ so that the pigment of absorption desorbs completely
L ultrapure water is re-dissolved as primverose solution to be measured, carries out HPLC measurement, the chromatostrip of HPLC measurement after crossing 0.45 μm of filter membrane
Part is as follows:
Chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm, 3.5 μm；Mobile phase: (A) 0.02M second
Sour ammonium；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；6.5-10 min, 32% B；10-14
Min, 32%-15% B；Flow velocity: 0.5mL/min, Detection wavelength: 254nm and 485nm, column temperature: 25 °C；Sample volume: 5 μ L.
Data processing: extracting the chromatogram of the synthetic dyestuff detected from HPLC, as shown in Figure 10, passes through what is detected
Peak area corresponding to synthetic dyestuff obtains the content of synthetic dyestuff in test sample by standard curve, then reality is calculated
The content of synthetic dyestuff in sample is determined by experiment and obtains and contain only a kind of this pigment of lemon yellow in primverose, and pigment contains
Amount are as follows: 1.26 μ g/g.
Embodiment 3
Application of the amination Metaporous silicon dioxide material in children's edible biscuits synthetic dyestuff assay, including following step
It is rapid:
The first step draws standard curve
The drafting mode of standard curve is identical with the drafting mode of 2 standard curve of embodiment；
Second step, the measurement of synthetic dyestuff content in children's edible biscuits
The children's edible biscuits sample for accurately weighing 1.0 g, is put into the centrifuge tube of 50 mL, and 20 are added wherein after smashing to pieces
ML ultrapure water is dissolved, and for quick, abundant dissolution, be can be heated to 60 °C and is stirred several minutes, after dissolution, be cooled to room
Temperature, centrifugation remove undissolved precipitating, supernatant are crossed to 0.45 μm of filter membrane later, takes out 10 mL conducts from filtrate later
Initial children's biscuit solution carries out enrichment absorption, and adsorption method is as follows: by the amination mesoporous silicon oxide adsorbent of 5-15 mg
It is added to ultrasound 10-15 min row enrichment absorption, centrifugal treating in filtrate and outwells supernatant, collect solid precipitating (solid precipitating
As it is adsorbed with the amination Metaporous silicon dioxide material of synthetic dyestuff), by the desorption solvent of 10mL, (desorption solvent is volume ratio
For the mixed solution of the B-R buffer solution of the acetone and pH=11 of 8:2) it is added to ultrasound desorption in above-mentioned solid precipitating, ultrasound solution
Suction can repeatedly carry out supernatant being collected by centrifugation later, dries up in mild nitrogen atmosphere so that the pigment adsorbed desorbing completely,
And 500 μ L ultrapure waters is used to re-dissolve as children's biscuit solution to be measured, HPLC measurement is carried out after crossing 0.45 μm of filter membrane, HPLC is surveyed
Fixed chromatographic condition is as follows:
Chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm, 3.5 μm；Mobile phase: (A) 0.02M second
Sour ammonium；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；6.5-10 min, 32% B；10-14
Min, 32%-15% B；Flow velocity: 0.5mL/min, the red Detection wavelength of sunset yellow, lemon yellow, amaranth, temptation is 254nm, orange
The Detection wavelength of Huang II is 485nm, column temperature: 25 °C；Sample volume: 5 μ L.
Data processing: extracting the chromatogram of the synthetic dyestuff detected from HPLC, as shown in figure 11, passes through what is detected
The chromatogram of synthetic dyestuff can be intuitive to see the chromatographic peak for not being found synthetic dyestuff, therefore judge to eat cake in children
In dry and synthetic dyestuff is not detected.
Embodiment 4
Application of the amination Metaporous silicon dioxide material in synthetic dyestuff purification, specifically used method are as follows: closed
In the waste liquid handled at pigment purification, amination Metaporous silicon dioxide material is added to waste liquid according to the solid-to-liquid ratio of 1:5 ~ 10
In, stirring a period of time；If range estimation or sample detection discovery waste liquid can take the circumstances into consideration to increase still containing more synthetic dyestuff
The additive amount of amination Metaporous silicon dioxide material.
Embodiment 5
Amination Metaporous silicon dioxide material can pass through after carrying out synthetic dyestuff assay or synthetic dyestuff purified treatment
Following manner regeneration: the mixed solution after amination Metaporous silicon dioxide material adsorption treatment is centrifugated on centrifuge,
The amination Metaporous silicon dioxide material for being adsorbed with synthetic dyestuff is deposited in the bottom of centrifuge tube, outwells supernatant, collects bottom
Solid precipitating, be added in desorption solvent, carry out ultrasonic desorption processing, by desorption solvent by amination mesoporous silicon oxide
The adsorbed synthetic dyestuff cleaning removal of material, then divided amination Metaporous silicon dioxide material and desorption solvent by centrifuge
From the above desorption process may be repeated repeatedly, then be put into the amination Metaporous silicon dioxide material after centrifuge separation very
In empty drying box, the dry 3h at 60 DEG C completes regeneration, reusable.
It should be noted last that: technical solution of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or locally replace that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (9)
1. a kind of preparation method of amination Metaporous silicon dioxide material, which is characterized in that disperse Metaporous silicon dioxide material
In appropriate solvent, it is then proportionally added into 3- aminopropyl trimethoxy siloxane, finally carries out heating reflux reaction, reaction knot
It is post-processed after beam up to amination Metaporous silicon dioxide material；
Wherein, the molar ratio of the Metaporous silicon dioxide material and 3- aminopropyl trimethoxy siloxane that are added is 3 ~ 6:1.
2. the preparation method of amination Metaporous silicon dioxide material according to claim 1, which is characterized in that specifically include
Following steps:
1) Metaporous silicon dioxide material is taken to be added in appropriate dehydrated alcohol in proportion, and ultrasonic disperse obtains reaction solution；
2) take 3- aminopropyl trimethoxy siloxane in proportion and be added dropwise in the reaction solution of step 2), then 90 ~
130 °C of lower heating reflux reaction 10-14 h；
3) solution after reacting is cooled to room temperature, and is collected by centrifugation solid precipitating, and with second alcohol and water after alternately washing is multiple, vacuum
Drying is to get amination Metaporous silicon dioxide material.
3. the amination Metaporous silicon dioxide material being prepared using preparation method of any of claims 1 or 2.
4. amination Metaporous silicon dioxide material is in synthetic dyestuff assay and synthetic dyestuff purification enrichment described in claim 3
In application, which is characterized in that the amination Metaporous silicon dioxide material is used as adsorbent.
5. application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay according to claim 4, special
Sign is, comprising the following steps:
1) it draws standard curve: the standard substance of a variety of synthetic dyestuffs being taken to be configured to a series of standard solution of concentration gradients respectively
And HPLC detection is carried out, regression analysis is then made to its concentration with peak area corresponding to the standard solution, is respectively obtained each
The concentration of standard solution of pigment and the standard curve of its peak area；
2) HPLC of synthetic dyestuff content is detected in sample to be tested: firstly, sample to be tested progress pre-treatment is obtained initial sample
The amination Metaporous silicon dioxide material, amination Metaporous silicon dioxide material is added in solution in the initial sample solution
In initial sample solution after the completion of evenly dispersed and absorption, the amination meso-porous titanium dioxide for being adsorbed with synthetic dyestuff is collected by centrifugation
Silicon materials；Then, it disperses the amination Metaporous silicon dioxide material that gained is adsorbed with synthetic dyestuff in desorption solvent and carries out
Parsing, parsing can be repeated several times, and thus synthetic dyestuff, which desorbs to be scattered in desorption solvent, obtains stripping workshop, later to solution
Solution is inhaled to be dried to obtain synthetic dyestuff sample；Gained synthetic dyestuff sample preparation is finally taken to obtain solution to be measured, it is to be measured molten
The volume of liquid can satisfy HPIC detection volume, carries out HPLC to the solution to be measured and detects to obtain peak area, control step
It is rapid 1) in standard curve, further calculate to obtain synthetic dyestuff content in sample to be tested.
6. application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay according to claim 5, special
Sign is that the synthetic dyestuff is azo synthetic dyestuff.
7. application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay according to claim 6, special
Sign is that the azo synthetic dyestuff includes sunset yellow, lemon yellow, amaranth, lures red and orange beta-naphthol.
8. application of the amination Metaporous silicon dioxide material in synthetic dyestuff assay according to claim 6, special
Sign is, the chromatographic condition of HPLC detection are as follows: chromatographic column: Agilent Eclipse Plus C18, specification: 4.6 × 100 mm,
3.5 µm；Mobile phase: (A) 0.02M ammonium acetate；(B) methanol, gradient elution ratio setting: 0-6.5 min, 15%-32% B；
6.5-10 min, 32% B；10-14 min, 32%-15% B；Flow velocity: 0.5mL/min；Sunset yellow, lemon yellow, amaranth, temptation
Red Detection wavelength is 254nm, and the Detection wavelength of orange beta-naphthol is 485nm.
9. the regeneration method of amination Metaporous silicon dioxide material, which is characterized in that the amination Metaporous silicon dioxide material
It can be regenerated by the following method after synthetic dyestuff assay and synthetic dyestuff purification enrichment use: after collecting absorption use
Amination Metaporous silicon dioxide material, is scattered in desorption solvent, ultrasonic treatment, is centrifugally separating to obtain amination Jie later
After being so repeated as many times, finally obtained amination Metaporous silicon dioxide material is dried for hole earth silicon material, i.e., complete
At regeneration.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0386926A2 (en) * | 1989-03-02 | 1990-09-12 | Supelco, Inc. | Silica gel supports suitable for chromatographic separations |
| CN101234329A (en) * | 2008-01-09 | 2008-08-06 | 华中科技大学 | SiO2 granule surface molecule print adsorption agent and preparation thereof |
| CN106693911A (en) * | 2017-02-13 | 2017-05-24 | 辽宁大学 | Functionalized silica adsorbent and application thereof in enrichment of silver ions in chlorinated wastewater |
| CN107381586A (en) * | 2017-07-19 | 2017-11-24 | 东南大学 | The method that silica nanoparticle surface modifies amino |
| CN107748210A (en) * | 2017-09-14 | 2018-03-02 | 昌邑市检验检测中心 | The method that HPLC DAD detect a variety of synthetic dyestuffs in wheaten food simultaneously |
| CN110290867A (en) * | 2017-02-22 | 2019-09-27 | 三菱化学株式会社 | Release agent, the release agent application and using the release agent steviol glycoside separation method and using the separation method steviol glycoside manufacturing method |
-
2018
- 2018-12-06 CN CN201811486896.3A patent/CN109482163A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0386926A2 (en) * | 1989-03-02 | 1990-09-12 | Supelco, Inc. | Silica gel supports suitable for chromatographic separations |
| CN101234329A (en) * | 2008-01-09 | 2008-08-06 | 华中科技大学 | SiO2 granule surface molecule print adsorption agent and preparation thereof |
| CN106693911A (en) * | 2017-02-13 | 2017-05-24 | 辽宁大学 | Functionalized silica adsorbent and application thereof in enrichment of silver ions in chlorinated wastewater |
| CN110290867A (en) * | 2017-02-22 | 2019-09-27 | 三菱化学株式会社 | Release agent, the release agent application and using the release agent steviol glycoside separation method and using the separation method steviol glycoside manufacturing method |
| CN107381586A (en) * | 2017-07-19 | 2017-11-24 | 东南大学 | The method that silica nanoparticle surface modifies amino |
| CN107748210A (en) * | 2017-09-14 | 2018-03-02 | 昌邑市检验检测中心 | The method that HPLC DAD detect a variety of synthetic dyestuffs in wheaten food simultaneously |
Non-Patent Citations (1)
| Title |
|---|
| PEIGE QIN ET AL.: "Amino-functionalized mesoporous silica nanospheres (MSN-NH2) as sorbent for extraction and concentration of synthetic dyes from foodstuffs prior to HPLC analysis", 《ANALYTICAL METHODS》 * |
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