CN108276584A - The detection method of aromatic amine compound in a kind of human urine - Google Patents
The detection method of aromatic amine compound in a kind of human urine Download PDFInfo
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Abstract
The present invention relates to a kind of detection methods of aromatic amine compound in human urine.This method is that sulfonic functional COFs materials are added and carry out Solid Phase Extraction, isolates solid formation, is eluted to solid formation using eluting solvent, obtain eluent after being pre-processed to human urine；Aromatic amine compound in eluent is measured；The sulfonic functional COFs materials include the covalent organic framework that 2,4,6 trifonnyl 1,3,5-trihydroxybenzene, 2,5 diamino benzene sulfonic acids are formed through Schiff condensation reaction.This method carries out Solid Phase Extraction using sulfonic functional COFs materials as adsorbent to the aromatic amine compound in human urine, selectivity efficient enrichment can be carried out to trace aromatic amine compounds in complex matrices using the characteristic of COFs materials, the pretreatment process that sample can be greatly simplified improves the detection efficiency and detection accuracy of aromatic amine compound.
Description
Technical field
The invention belongs to the detection fields of aromatic amine compound, and in particular to aromatic amine compound in a kind of human urine
Detection method.
Background technology
Some aromatic amine compounds have carcinogenic and mutagenic effect, can be by sucking, eating or penetrating skin
It absorbs and causes to be poisoned.Include in harmful substance and potential hazard substance list (HPHCs) in FDA cigarette products and cigarette smoke
6 kinds of aromatic amines, 4- aminobphenyls, 1- amino naphthalenes, 2- amino naphthalenes, o-anisidine, 2,6- dimethylanilines, ortho-aminotoluene.These
Aromatic amine compounds are exposed biomarker as cigarette smoke.
The property and journey of health risk when being conducive to illustrate that the mankind are exposed to substance of this kind for the research of biomarker
Degree.Since aromatic amine biomarker content is relatively low, when detection interfere it is larger, it is more demanding to the pre-treatment of sample.Urine can
The exposure for effectively reflecting recent environmental contaminants multipath has the analysis and research of aromatic amine compound in urine and represents very much
Meaning.(the Detection of carcinogenic aromatic amines in the urine of non-such as Grimmer
smokers.Sci Total Environ,2000,247(1):Urine 81-90) is handled with enzymatic isolation method, is spread out using pentafluoropropionic anhydride
Biochemical reaction and GC-MS methods, analyze the aromatic amine in urine.(the Determination of three such as Riedel
carcinogenic aromatic amines in urine of smokers and nonsmokers.J Anal
Toxicol,2006,30(3):The σ-in smoker and non-smoker's urine sample 187-195) is had detected using derivatization-GC-MS methods
Toluidines, 2- amino naphthalenes and 4- aminobphenyls.Because needing derivative reaction, sample pre-treatments are very cumbersome to be taken GC-MS methods.
Publication No. is that the patent application of CN102788852A discloses a kind of Liquid Chromatography-Tandem Mass Spectrometry detection Human Urine
The wherein method of aromatic amine compound in liquid is to utilize dense HCl/water solution urine, and purified by PAH molecular blotting columns
Processing, is then analyzed using LC-MS/MS.This method can simplify sample pre-treatments step, improve analysis efficiency, but quotient
The PAH molecular blotting columns of product are polycyclic aromatic hydrocarbon (PAHs) molecular blotting column, and non-aromatic amine molecular blotting column, there are selectivity
Not high problem.
The detection method of existing aromatic amine compounds is led because adsorbent is poor to the selective absorption of aromatic amine compound
Cause detection efficiency and the detection accuracy of aromatic amine compound to be improved.
Invention content
It is existing to solve the purpose of the present invention is to provide a kind of detection method of aromatic amine compound in human urine
The poor problem of detection efficiency and detection accuracy existing for detection method.
To achieve the above object, the technical solution adopted in the present invention is：
The detection method of aromatic amine compound, includes the following steps in a kind of human urine：Human urine is located in advance
After reason, be added sulfonic functional COFs materials carry out Solid Phase Extraction, isolate solid formation, using eluting solvent to solid formation into
Row elution, obtains eluent；Aromatic amine compound in eluent is measured；
The sulfonic functional COFs materials include 2,4,6- trifonnyls 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids warp
The covalent organic framework that Schiff condensation reaction is formed.
The detection method of aromatic amine compound in the human urine of the present invention, using sulfonic functional COFs materials as suction
Attached dose carries out Solid Phase Extraction to the aromatic amine compound in human urine, can play the role of following：The aperture confinement of COFs materials
Effect can exclude the absorption of the macromoleculars such as protein in urine matrix；Sulfonic group on COFs materials and aromatic amine compounds
Amino electrostatic adsorption it is strong, with efficient absorption aromatic amine compounds and the absorption of elecrtonegativity compound can be prevented；
Benzene ring structure on COFs materials and there is strong Π-Π effects between the phenyl ring of aromatic amine compounds, in being total to for factors above
The selectivity efficient enrichment of trace aromatic amine compounds in complex matrices is realized under same-action.The COFs materials are applied to
The detection of aromatic amine compound in human urine, can greatly simplify the pretreatment process of sample, improve the inspection of aromatic amine compound
Survey efficiency and detection accuracy.
Above-mentioned sulfonic functional COFs materials are prepared by method comprising the following steps：By 2,4,6- trifonnyls
1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids carry out in a solvent Schiff condensation reaction to get.Preferably, 2,4,6- front threes
Acyl group 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids weight ratio be (10-30)：(10-40).
The magnetic nano-particle of amino functional can further be added in above-mentioned Schiff condensation reaction, pass through amino
With reacting for aldehyde radical, magnetic nano-particle is modified onto covalent organic framework, to make covalent organic framework have centainly
Magnetism forms magnetic sulfonic functional COFs materials.
The magnetism sulfonic functional COFs materials, including 2,4,6- trifonnyl 1,3,5-trihydroxybenzene, 2,5- diaminobenzenes
The covalent organic framework that sulfonic acid is formed through Schiff condensation reaction, and modify to the magnetic nano particle on covalent organic framework
Son, the magnetic nano-particle are the Fe of amino functional3O4/SiO2Core-shell nano.
The Fe of the amino functional3O4/SiO2Core-shell nano is with Fe3O4For core, with SiO2It, can be according to existing for shell
It is prepared by technology.Preferably, the Fe of the amino functional3O4/SiO2Core-shell nano is by method comprising the following steps
It is prepared：
A) with nanometer Fe3O4Particle is core, and ethyl orthosilicate is silicon source, and Fe is prepared using stober methods3O4@SiO2Nucleocapsid is received
Rice corpuscles；
B) by Fe3O4@SiO2Core-shell nano is dispersed in toluene, and the first of 3- TSL 8330s is added
Benzole soln carry out coupling reaction to get.
In step a), per 1.0-4.0g nanometer Fes3O4Particle, which corresponds to, uses 1-5mL ethyl orthosilicates.Stober methods are used
Mixed solvent by absolute ethyl alcohol, water, concentrated ammonia liquor by volume (50-200)：(20-60)：(1-5) is mixed, concentrated ammonia liquor
A concentration of 25-28wt%.
Preferably, the nanometer Fe3O4Particle is made by method comprising the following steps：FeCl3·6H2O and anhydrous acetic acid
Sodium carries out hydro-thermal reaction to get the nanometer Fe in ethylene glycol solvent3O4Particle.FeCl3·6H2The matter of O and anhydrous sodium acetate
Amount is than being (1.0-3.0)：(2.0-5.0).The hydro-thermal reaction is to react 5-10h at 190-210 DEG C.
In step b), per 0.2-2.0g Fe3O4@SiO2Core-shell nano, which corresponds to, is added 3- aminopropyl trimethoxy silicon
The mass concentration of the toluene solution of toluene solution 5-20mL, the 3- TSL 8330 of alkane is 5-20%.The idol
Connection reaction is the back flow reaction 20-30h at 100-120 DEG C.
2,4,6- trifonnyls 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids, magnetic nano-particle weight ratio be (10-
30)：(10-40)：(10-50).The selective enrichment effect that the COFs materials of reaction preparation are carried out with the proportioning reaches best.
Following technical scheme can be used in the preparation method of above-mentioned magnetism sulfonic functional COFs materials：
A kind of preparation method of magnetism sulfonic functional COFs materials, including：By 2,4,6- trifonnyls 1,3,5-trihydroxybenzene,
2,5- diamino benzene sulfonic acids, magnetic nano-particle carry out in a solvent Schiff condensation reaction to get.
The solvent is trimethylbenzene and dioxane by volume 1：The mixed solvent of (3-6) composition.
The Schiff condensation reaction carries out under conditions of acetic acid is catalyst.Preferably, the addition quality of acetic acid
For 2,4,6- trifonnyls 1,3,5-trihydroxybenzene, the 5-50% of 2,5- diamino benzene sulfonic acids, magnetic nano-particle gross mass.
The Schiff condensation reaction is to react 60-80h at 90-120 DEG C.
The magnetic sulfonic functional COFs materials prepared using above-mentioned preferred parameter, product quality stability is good, to urine
Aromatic amine compounds in liquid have splendid selectivity efficient enrichment, can be conveniently used for aromatic amine in human urine
In the analyte detection process of compound.
Above-mentioned magnetism sulfonic functional COFs materials have good application in magnetic solid phase extraction.
Contain magnetic nano-particle in the magnetism sulfonic functional COFs materials, is selected to aromatic amine compounds
After the enrichment of selecting property, phase separation can be realized by external magnetic field, it is easy to operate, quick, enormously simplify aromatic amine compounds
Testing process, save the plenty of time simultaneously reduce cost.
By taking the magnetic solid phase extraction of aromatic amine compounds in human urine as an example, urine is handled through concentrated hydrochloric acid or enzymolysis processing
Afterwards, the selective enrichment that magnetic sulfonic functional COFs materials carry out aromatic amine compounds is added, utilizes magnetic fields point
The magnetic sulfonic functional COFs materials after absorption are separated out, are then eluted using eluting solvent, gained eluent
It is used as sample solution.
It, can be by making magnetic sulfonic functional using magnet in the outside of container during above-mentioned magnetic solid phase extraction
COFs materials are convenient and liquid phase separation, the processes such as washing, elution greatly simplify.
The present invention additionally provides above-mentioned magnetic sulfonic functional COFs materials aromatic amine compounds in human urine to examine
Application in terms of survey.
After being pre-processed to human urine, magnetic sulfonic functional COFs materials are added and carry out magnetic solid phase extraction,
The magnetic sulfonic functional COFs materials for being adsorbed with determinand are isolated under magnetic fields, are eluted using eluting solvent,
Obtain eluent；HPLC-MS/MS analyses are carried out after eluent is concentrated.
The pretreatment is that concentrated hydrochloric acid is added into human urine, and after handling 0.5-2h at 60~80 DEG C, it is molten that NaOH is added
It is neutrality that liquid, which adjusts pH value, and ammonium acetate-ammonium hydroxide buffer solution that pH=7.0 is then added is mixed.
Preferably, the concentrated hydrochloric acid 0.1-1mL that mass concentration is 36-38% is added per 1-5mL human urines.Per 1-5mL people
It is 5-10mL that body urine, which corresponds to and the volume of ammonium acetate-ammonium hydroxide buffer solution is added,；It is corresponding that magnetic sulfonic functional COFs is added
The quality of material is 100-500mg.
The time of magnetic solid phase extraction is 0.5-1h.The eluting solvent dilutes concentrated ammonia liquor by methanol, concentrated ammonia liquor
A concentration of 25-28wt%, a concentration of 2-7wt% of ammonia in eluting solvent.It is eluted using 5-20mL eluting solvents, by gained
Eluent is concentrated to 0.1-1mL.
The detection of aromatic amine compound in human urine is carried out using this method, magnetic sulfonic functional COFs materials
The more commercial solid-phase extraction column of cost substantially reduces, and testing process greatly simplifies, improve aromatic amine compound detection efficiency and
Detection accuracy.
Description of the drawings
Fig. 1 is the synthesis schematic diagram of magnetic sulfonic functional COFs materials；
Fig. 2 is the fundamental diagram of magnetic solid phase extraction process.
Specific implementation mode
Embodiments of the present invention are described further with reference to specific embodiment.Magnetic Nano in following embodiment
Particle is prepared according to the following steps：
A) by 1.35gFeCl3·6H2O and 3.6g anhydrous sodium acetates are dissolved into 35mL ethylene glycol, magnetic agitation mixture
To solid-solution, solution is transferred in hydrothermal reaction kettle, hydro-thermal reaction 8h at 200 DEG C, is separated by solid-liquid separation, use is a concentration of
Dilute hydrochloric acid washing, the drying of 0.1mol/L, obtains nanometer Fe3O4Particle；
B) nanometer Fe3O4Particle (4.0g) is evenly spread to by absolute ethyl alcohol (160mL), deionized water (40mL) and dense ammonia
In the mixed liquor of water (28wt%, 3mL) composition, TEOS (2mL) reactions are added dropwise under agitation, obtain Fe3O4@SiO2
Nano-particle；
C) by 1.0g Fe3O4@SiO2Nano-particle is dispersed in 100mL dry toluenes, in N2Under protection, it is added dropwise a concentration of
The anhydrous toluene solution 10mL of the 3- TSL 8330s of 10wt%, back flow reaction is for 24 hours to get ammonia at 110 DEG C
The Fe of base functionalization3O4/SiO2Core-shell nano.
Embodiment 1
The magnetic sulfonic functional COFs materials of the present embodiment, as shown in Figure 1, being prepared using following steps：
2,4,6- trifonnyls 1,3,5-trihydroxybenzene (21.0mg), 2,5- diamino benzene sulfonic acids (28.2mg) are dissolved in trimethyl
In benzene/dioxane mixed solvent (being mixed by 0.2mL trimethylbenzenes, 0.8mL dioxanes), it is added
The acetic acid solution of a concentration of 3mol/L of 0.1mL, is mixed to form uniform solution at room temperature；Then under the conditions of nitrogen protection, add
Enter 0.02g magnetic nano-particles, 72h is reacted at 100 DEG C, black solid product is isolated after reaction, uses anhydrous dimethyl base successively
After formamide, anhydrous tetrahydro furan and anhydrous propanone washing, washs 2-3 times with absolute methanol and complete activation, it is true at 150 DEG C
The dry 12h of sky is to get magnetic sulfonic functional COFs materials.
The magnetic sulfonic functional COFs materials of the present embodiment are applied to the inspection of aromatic amine compound in human urine
It surveys, includes the following steps：
1) magnetic solid phase extraction：The urine sample stored in -18 DEG C is taken out and is thawed at room temperature, the urine sample for taking 5mL to thaw
It is placed in plastic centrifuge tube, 1mL concentrated hydrochloric acid solutions is added, handles 2h in 80 DEG C of waters bath with thermostatic control, then cools to room temperature, be added
It is 7.0 that the NaOH solution of a concentration of 10mol/L of 1.2mL, which is neutralized to pH value, and 10mL a concentration of 0.5mol/L, pH=are added later
7.0 ammonium acetate-ammonium hydroxide buffer solution is uniformly mixed, and obtains sample solution；
Sample solution is transferred in 50mL beakers, 100 μ L D7-1- amino naphthalenes (a concentration of 50ng/mL) and D9- is added
4- aminobphenyls (a concentration of 10ng/mL) mix magnetic force after inner mark solution and 100mg magnetism sulfonic functional COFs materials
30min is stirred, magnet is placed in the outer wall of beaker side keeps the magnetic sulfonic functional COFs materials after absorption real with solution
It is now separated, topples over solution in beaker；Magnet is removed, 10mL water is added into beaker and is washed, magnetic agitation 10min, then
After the secondary realization phase separation using magnet, washings are poured out；The eluting solvent of 10mL is added into beaker (by methanol to concentrated ammonia liquor
It dilutes, a concentration of 28wt% of concentrated ammonia liquor；A concentration of 5wt% of ammonia in eluting solvent), after magnetic agitation 10min, use
Magnet realizes phase separation, topples over collection eluent；Eluent is concentrated to after 0.1mL and is used as solution for later use to be measured, process signal
Figure is as shown in Figure 2；
2) HPLC-MS/MS is analyzed：The standard working curve that each target compound is established using internal standard method, by solution to be measured
Into HPLC-MS/MS Instrumental Analysis, detection data is substituted into standard working curve, 1- amino naphthalenes in sample, 2- amino is calculated
The concentration of naphthalene, 3- aminobphenyls, 4- aminobphenyls.
In step 2), the chromatographic condition of HPLC-MS/MS analyses is：Spectrum column is Waters C18 (100mm × 2.1mm
I.d., 2.7 μm), column temperature：30℃；Mobile phase A is the aqueous solution containing 0.1% formic acid, and Mobile phase B is the acetonitrile containing 0.1% formic acid
Solution；Using gradient elution, condition is as follows：0-3min, 100%A0%B；3.1-16.0min, 75%A25%B；16.1-
20min, 0%A100%B；20.1-25.0min 100%A；10 μ L of sampling volume；200 μ L/min of flow velocity.
Mass Spectrometry Conditions are：Ion source：Electron spray ionisation source (ESI)；Scan mode：Cation scans；Detection mode：It is mostly anti-
MRM should be monitored；Electron spray voltage：5500V；Gas curtain atmospheric pressure：30psi；Assist 1 pressure of gas：70psi；Assist 2 pressure of gas：
70psi；Ion source temperature：500℃；The quota ion pair of each compound, qualitative ion pair, residence time, collision energy (CE)
And go cluster voltage (DP) referring to table 1.The quota ion pair of 1 each compound of table, qualitative ion pair, residence time, collision energy and
Remove cluster voltage
It is that detection limits that table 2, which is shown with 3 times of signal-to-noise ratio (S/N), and 10 times of S/N are the line of each aromatic amine compound of quantitative limit
Property equation, related coefficient, detection limit and quantitative limit.
Linear equation, related coefficient, detection limit and the quantitative limit of 2 aromatic amine compound of table
Same urine sample is carried out in one day to 6 parallel determinations and point is measured within 5 days, the relative standard deviation of measurement result
(RSD) withinday precision and day to day precision for indicating this method are carried out at the same time recovery of standard addition experiment, and the results are shown in Table 3.
Withinday precision, day to day precision and the rate of recovery of the method for 3 embodiment 1 of table
The precision of this method is good it can be seen from the result of table 3, recovery of standard addition is high, fragrant suitable for human urine
The detection of fragrant amine metabolin.
5 smokers and 2 non-smoker's urine samples are collected, using the method in embodiment 1, in urine sample
1- amino naphthalenes, 2- amino naphthalenes, 3- aminobphenyls, 4- aminobphenyl metabolins carry out magnetic solid phase extraction and HPLC-MS/MS analyses,
The results are shown in Table 4.
The urine sample of 4 smoker of table and non-smoker analyze (pg/mL)
As can be seen that 1- amino naphthalenes, 2- amino naphthalenes, 3- in human urine can be facilitated in detection using the method for embodiment 1
The content of aminobphenyl, 4- aminobphenyl metabolins, detection process is simple, detects precision and stability is good；In table 4, smoking
Aromatic amine metabolite content is apparently higher than non-smoker in person's urine, the purified treatment obtained using the magnetic solid phase extraction technology
Liquid may be that good basis is laid in the follow-up study of aromatic amine compound.
Embodiment 2
The magnetic sulfonic functional COFs materials of the present embodiment, are prepared using following steps：
2,4,6- trifonnyls 1,3,5-trihydroxybenzene (11.0mg), 2,5- diamino benzene sulfonic acids (18.2mg) are dissolved in trimethyl
In benzene/dioxane mixed solvent (being mixed by 0.2mL trimethylbenzenes, 0.6mL dioxanes), it is added
The acetic acid solution of a concentration of 3mol/L of 0.1mL, is mixed to form uniform solution at room temperature；Then under the conditions of nitrogen protection, add
Enter 0.02g magnetic nano-particles, 80h is reacted at 90 DEG C, black solid product is isolated after reaction, uses anhydrous dimethyl Ji Jia successively
After amide, anhydrous tetrahydro furan and anhydrous propanone washing, washs 2-3 times with absolute methanol and complete activation, the vacuum at 150 DEG C
Dry 12h is to get magnetic sulfonic functional COFs materials.
Embodiment 1 can refer to the detection method of aromatic amine compound in human urine using the COFs of the present embodiment, have
Body detection result is suitable with embodiment 1.
Embodiment 3
The magnetic sulfonic functional COFs materials of the present embodiment, are prepared using following steps：
2,4,6- trifonnyls 1,3,5-trihydroxybenzene (28.0mg), 2,5- diamino benzene sulfonic acids (40.0mg) are dissolved in trimethyl
In benzene/dioxane mixed solvent (being mixed by 0.2mL trimethylbenzenes, 1.2mL dioxanes), it is added
The acetic acid solution of a concentration of 3mol/L of 0.1mL, is mixed to form uniform solution at room temperature；Then under the conditions of nitrogen protection, add
Enter 0.04g magnetic nano-particles, 60h is reacted at 120 DEG C, black solid product is isolated after reaction, uses anhydrous dimethyl base successively
After formamide, anhydrous tetrahydro furan and anhydrous propanone washing, washs 2-3 times with absolute methanol and complete activation, it is true at 150 DEG C
The dry 12h of sky is to get magnetic sulfonic functional COFs materials.
Embodiment 1 can refer to the detection method of aromatic amine compound in human urine using the COFs of the present embodiment, have
Body detection result is suitable with embodiment 1.
Embodiment 4
The sulfonic functional COFs materials of the present embodiment, are prepared using following steps：By 2,4,6- trifonnyls
1,3,5-trihydroxybenzene (21.0mg), 2,5- diamino benzene sulfonic acids (28.2mg) be dissolved in trimethylbenzene/dioxane mixed solvent (by
0.2mL trimethylbenzenes, 0.8mL dioxanes mix) in, the acetic acid solution of a concentration of 3mol/L of 0.1mL is added,
It is mixed to form uniform solution at room temperature；Then under the conditions of nitrogen protection, 72h is reacted at 100 DEG C, and solid production is isolated after reaction
Object is washed 2-3 times after being washed successively with anhydrous dimethyl formamide, anhydrous tetrahydro furan and anhydrous propanone with absolute methanol
Activation is completed, 12h is dried in vacuo at 150 DEG C to get sulfonic functional COFs materials.
The sulfonic functional COFs materials of embodiment 4 in the detection of aromatic amine compound in applied to human urine,
Specific steps can refer to embodiment 2, differ only in step 1), (such as filters, centrifuges) using conventional solid-liquid separation means
Sulfonic functional COFs materials after absorption are detached from liquid phase, is then eluted, is eluted using eluting solvent
Liquid carries out subsequent analysis, based on the architectural characteristic of sulfonic functional COFs, to the aromatic amine compound in human urine
Good selectivity efficient enriched character is kept, highly sensitive and high efficient detection is carried out so as to application this method.
In the other embodiment of the sulfonic functional COFs materials of the present invention, 2,4,6- trifonnyl 1,3,5-trihydroxybenzene,
The dosage of 2,5- diamino benzene sulfonic acids, magnetic nano-particle and catalyst acetic acid, the condition of specific Schiff condensation reaction
It can be adaptively adjusted in the framework of the present definition, available can comparable COFs materials.
Claims (10)
1. the detection method of aromatic amine compound in a kind of human urine, which is characterized in that include the following steps：To human urine
After being pre-processed, sulfonic functional COFs materials are added and carry out Solid Phase Extraction, isolates solid formation, uses eluting solvent pair
Solid formation is eluted, and eluent is obtained；Aromatic amine compound in eluent is measured；
The sulfonic functional COFs materials include 2,4,6- trifonnyls 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids warp
The covalent organic framework that Schiff condensation reaction is formed.
2. the detection method of aromatic amine compound in human urine as described in claim 1, which is characterized in that 2,4,6- front threes
Acyl group 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids weight ratio be (10-30)：(10-40).
3. the detection method of aromatic amine compound in human urine as described in claim 1, which is characterized in that the sulfonic group
Functionalization COFs materials further include the magnetic nano-particle modified on the covalent organic framework, and the magnetic nano-particle is
The Fe of amino functional3O4/SiO2Core-shell nano.
4. the detection method of aromatic amine compound in human urine as claimed in claim 3, which is characterized in that the sulfonic group
Functionalization COFs materials are prepared by method comprising the following steps：By 2,4,6- trifonnyls 1,3,5-trihydroxybenzene, 2,5- diaminos
Base benzene sulfonic acid, magnetic nano-particle carry out in a solvent Schiff condensation reaction to get.
5. the detection method of aromatic amine compound in human urine as claimed in claim 4, which is characterized in that the solvent is
Trimethylbenzene and dioxane by volume 1：The mixed solvent of (3-6) composition.
6. the detection method of aromatic amine compound in human urine as claimed in claim 4, which is characterized in that 2,4,6- front threes
Acyl group 1,3,5-trihydroxybenzene, 2,5- diamino benzene sulfonic acids, magnetic nano-particle weight ratio be (10-30)：(10-40)：(10-50).
7. the detection method of aromatic amine compound in human urine as described in claim 1 or 4, which is characterized in that described
Schiff condensation reaction is to react 60-80h at 90-120 DEG C.
8. the detection method of aromatic amine compound in human urine as described in claim 1, which is characterized in that the pretreatment
It is that concentrated hydrochloric acid is added into human urine, after handling 0.5-2h at 60~80 DEG C, it is neutrality that NaOH solution adjustment pH value, which is added, so
Ammonium acetate-ammonium hydroxide buffer solution that pH=7.0 is added afterwards is mixed.
9. the detection method of aromatic amine compound in human urine as described in claim 1, which is characterized in that the elution is molten
Agent dilutes concentrated ammonia liquor by methanol, a concentration of 25-28wt% of concentrated ammonia liquor, a concentration of 2-7wt% of ammonia in eluting solvent.
10. the detection method of aromatic amine compound in human urine as described in claim 1, which is characterized in that the measurement
It is progress HPLC-MS/MS analyses after concentrating eluent.
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Cited By (10)
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| CN108997590A (en) * | 2018-07-16 | 2018-12-14 | 东华理工大学 | A kind of organic covalent framework material of the two-dimensional layer containing sulfonic acid group and preparation method thereof |
| CN110215904A (en) * | 2019-06-14 | 2019-09-10 | 河南中医药大学 | Magnetic carboxylated covalent organic framework nanocomposite and its preparation method and application |
| CN110672760A (en) * | 2019-11-18 | 2020-01-10 | 重庆市计量质量检测研究院 | Method for detecting decomposable harmful aromatic amine dye in textile |
| CN111530437A (en) * | 2020-05-18 | 2020-08-14 | 河南中医药大学 | Sulfonic acid functionalized covalent organic framework magnetic composite material with mixed action mode and preparation method and application thereof |
| CN112679731A (en) * | 2020-12-21 | 2021-04-20 | 同济大学 | Covalent organic framework material containing sulfonic acid group and preparation and application thereof |
| CN113854286A (en) * | 2021-09-18 | 2021-12-31 | 湖南大学 | Chlorine dioxide sustained release agent and preparation method and application thereof |
| CN114062584A (en) * | 2021-11-17 | 2022-02-18 | 中国检验检疫科学研究院 | Method for detecting methoxy acrylate bactericide, kit and application thereof |
| CN114216951A (en) * | 2021-12-08 | 2022-03-22 | 中国石油大学(北京) | Separation method of sulfonate compounds in sewage and analysis method of soluble organic matter molecule composition |
| CN114773482A (en) * | 2022-05-13 | 2022-07-22 | 太原理工大学 | Method for realizing rapid adsorption of biomolecules to cationic covalent organic framework by utilizing electrostatic interaction |
| CN115078564A (en) * | 2022-05-06 | 2022-09-20 | 沈阳药科大学 | Method for ultra-fast quantifying amine substances in urine |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108997590A (en) * | 2018-07-16 | 2018-12-14 | 东华理工大学 | A kind of organic covalent framework material of the two-dimensional layer containing sulfonic acid group and preparation method thereof |
| CN110215904B (en) * | 2019-06-14 | 2022-04-01 | 河南中医药大学 | Magnetic carboxylated covalent organic framework nano composite material and preparation method and application thereof |
| CN110215904A (en) * | 2019-06-14 | 2019-09-10 | 河南中医药大学 | Magnetic carboxylated covalent organic framework nanocomposite and its preparation method and application |
| CN110672760A (en) * | 2019-11-18 | 2020-01-10 | 重庆市计量质量检测研究院 | Method for detecting decomposable harmful aromatic amine dye in textile |
| CN111530437A (en) * | 2020-05-18 | 2020-08-14 | 河南中医药大学 | Sulfonic acid functionalized covalent organic framework magnetic composite material with mixed action mode and preparation method and application thereof |
| CN111530437B (en) * | 2020-05-18 | 2023-10-20 | 河南中医药大学 | Sulfonic acid functionalized covalent organic framework magnetic composite material with mixed action mode and preparation method and application thereof |
| CN112679731A (en) * | 2020-12-21 | 2021-04-20 | 同济大学 | Covalent organic framework material containing sulfonic acid group and preparation and application thereof |
| CN113854286A (en) * | 2021-09-18 | 2021-12-31 | 湖南大学 | Chlorine dioxide sustained release agent and preparation method and application thereof |
| CN114062584A (en) * | 2021-11-17 | 2022-02-18 | 中国检验检疫科学研究院 | Method for detecting methoxy acrylate bactericide, kit and application thereof |
| CN114062584B (en) * | 2021-11-17 | 2024-02-02 | 中国检验检疫科学研究院 | Method for detecting methoxy acrylic acid ester bactericide, kit and application thereof |
| CN114216951A (en) * | 2021-12-08 | 2022-03-22 | 中国石油大学(北京) | Separation method of sulfonate compounds in sewage and analysis method of soluble organic matter molecule composition |
| CN115078564A (en) * | 2022-05-06 | 2022-09-20 | 沈阳药科大学 | Method for ultra-fast quantifying amine substances in urine |
| CN115078564B (en) * | 2022-05-06 | 2024-05-31 | 沈阳药科大学 | Method for quantifying amine substances in urine at ultra-fast speed |
| CN114773482A (en) * | 2022-05-13 | 2022-07-22 | 太原理工大学 | Method for realizing rapid adsorption of biomolecules to cationic covalent organic framework by utilizing electrostatic interaction |
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