CN109507317A - A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent - Google Patents
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent Download PDFInfo
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- CN109507317A CN109507317A CN201811377578.3A CN201811377578A CN109507317A CN 109507317 A CN109507317 A CN 109507317A CN 201811377578 A CN201811377578 A CN 201811377578A CN 109507317 A CN109507317 A CN 109507317A
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- organic framework
- metal organic
- framework material
- gallium
- gallium metal
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- 239000000463 material Substances 0.000 title claims abstract description 106
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 96
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 93
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 50
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 30
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229930185605 Bisphenol Natural products 0.000 claims description 22
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 22
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 20
- 150000002259 gallium compounds Chemical class 0.000 claims description 18
- 229940106691 bisphenol a Drugs 0.000 claims description 14
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 12
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 10
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 6
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229940044658 gallium nitrate Drugs 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011896 sensitive detection Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000012086 standard solution Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000004448 titration Methods 0.000 description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000013110 organic ligand Substances 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
-
- 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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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to trace object detection technique fields, more particularly, to a kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent.Gallium metal organic framework material has good sensing capability to incretion interferent in the present invention, can get sensitive detection and accurate detection result.
Description
Technical field
The present invention relates to trace object detection technique fields, are examining more particularly, to a kind of gallium metal organic framework material
Survey the Application in Sensing in incretion interferent.
Background technique
Incretion interferent (Endocrine Disrupting Chemicals, i.e. EDCs), also referred to as environmental hormone
(Environmental Hormone) is a kind of chemical substance of exogenous disturbance endocrine system, by taking in, accumulating
Various approach do not bring anomalous effects to organism directly as noxious material, but similar estrogen acts as organism
With even if quantity is few, capable of also allowing the endocrine imbalance of organism, various abnormal phenomenon occur.Up to the present, have a large amount of
Analysis method be used to detect EDCs in various sample substrates, such as liquid chromatogram, liquid chromatography-tandem mass spectrometry, gas-chromatography-
The detection method of mass spectrum etc., the authenticity for EDCs measure.However, in order to obtain sensitive detection and accurately as a result, multiple
Miscellaneous and cumbersome sample pretreatment program is essential.Detection method be related to expensive instrument, complicated preparation step or
Time cost.Therefore, quickly, sensitively the method for detection EDCs is increasingly taken seriously.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
It is an object of the present invention to provide a kind of biography of gallium metal organic framework material in detection incretion interferent
Induction is used, and is related to expensive instrument, complicated preparation to solve the detection method of incretion interferent existing in the prior art
The problem of step or time cost.The gallium metal organic framework material synthesized in the present invention has excellent physical property and chemistry
The functional material of the superelevation porosity of property, porosity have the latent of very big absorption and separation dangerous substance in surrounding medium
Power.Newly synthesized gallium metal organic framework material has good sensing capability to incretion interferent in the present invention, with gallium gold
Belong to organic framework material and detect incretion interferent, can get sensitive detection and accurate testing result.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent.
Preferably, the incretion interferent is selected from repefral, diethyl phthalate, bisphenol-A, double
At least one of phenol B, Bisphenol F, bisphenol AF, bisphenol S and bisphenol fluorene.
Preferably, the gallium metal organic framework material is prepared by pyromellitic acid, trivalent gallium compound and water.
Preferably, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-4:6-8:450-
650。
Preferably, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-3.5:7-7.5:
500-560。
Preferably, the trivalent gallium compound is selected from one of gallium nitrate or gallium sulfate.
Preferably, the gallium metal organic framework material preparation method the following steps are included:
Pyromellitic acid, trivalent gallium compound and water are mixed and reacted, gallium metal organic framework material is obtained.
Preferably, the temperature of the reaction is 190-210 DEG C, more preferably 195-205 DEG C；
Preferably, the reaction time is 22-48h.
Preferably, the reaction time is 24-30h.
Compared with the prior art, the invention has the following beneficial effects:
Newly synthesized gallium metal organic framework material has excellent physical property, chemical property and superelevation hole in the present invention
The functional material of gap rate, porosity have the potentiality of very big absorption and separation dangerous substance, gallium of the invention in surrounding medium
Metal-organic framework materials are in the Application in Sensing for detecting incretion interferent, to bisphenol-A, repefral, adjacent benzene two
Formic acid diethylester, bisphenol b, Bisphenol F, bisphenol AF, bisphenol S and bisphenol fluorene have good sensing capability, can sensitively be examined
It surveys, and obtains accurate detection result.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that repefral of the present invention titrates gallium metal organic framework material solution fluorescence Strength Changes song
Line；
Fig. 2 is that diethyl phthalate of the present invention titrates gallium metal organic framework material solution fluorescence Strength Changes song
Line；
Fig. 3 is that bisphenol-A of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
Fig. 4 is that bisphenol b of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
Fig. 5 is that Bisphenol F of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
Fig. 6 is that bisphenol AF of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
Fig. 7 is that bisphenol S of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
Fig. 8 is that bisphenol fluorene of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent.
The present invention detects incretion interferent using gallium metal organic framework material, can get sensitive detection and accurately
Testing result.
Preferably, the incretion interferent is selected from repefral, diethyl phthalate, bisphenol-A, double
At least one of phenol B, Bisphenol F, bisphenol AF, bisphenol S and bisphenol fluorene.
Gallium metal organic framework material dimethyl terephthalate, diethyl phthalate, bis-phenol in the present invention
A, a variety of incretion interferents such as bisphenol b have excellent sensing capabilities, can dimethyl terephthalate, phthalic acid two
The incretion interferents such as ethyl ester, bisphenol-A are sensitively detected, and accurate detection result can be obtained.
Metal-organic framework materials have excellent physical property and chemical property, and high porosity has in surrounding medium
The potentiality of very big absorption and separation dangerous substance.Newly synthesized gallium metal organic framework material has excellent change in the present invention
Stability and ratio of briquetting are learned, incretion interferent is detected and is removed, detection sensitivity with higher and accurately knot
Fruit.
Preferably, the gallium metal organic framework material is prepared by pyromellitic acid, trivalent gallium compound and water.
The newly synthesized gallium metal organic framework material of the present invention is prepared by pyromellitic acid, trivalent gallium compound and water,
Chemical stability is high.
Preferably, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-4:6-8:450-
650。
The ratio of metal ion and organic ligand largely affects the physical property of metal-organic framework materials
And chemical property.It uses molar ratio for the pyromellitic acid of 3-4:6-8:450-650, trivalent gallium compound and water in the present invention, obtains
The gallium metal organic framework material arrived has excellent chemical stability and ratio of briquetting.
Preferably, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-3.5:7-7.5:
500-560。
By further preferred pyromellitic acid, the molar ratio of trivalent gallium compound and water, it can get ratio of briquetting and chemistry be steady
Qualitative better gallium metal organic framework material.
Preferably, the trivalent gallium compound is selected from one of gallium nitrate or gallium sulfate.
Preferably, the gallium metal organic framework material preparation method the following steps are included:
Pyromellitic acid, trivalent gallium compound and water are mixed and reacted, gallium metal organic framework material is obtained.
The preparation method of gallium metal organic framework material is easy to operate in the present invention, and cost is relatively low.
Preferably, the temperature of the reaction is 190-210 DEG C, more preferably 195-205 DEG C.
The temperature of reaction it is typical but non-limiting be, for example, 190 DEG C, 191 DEG C, 192 DEG C, 193 DEG C, 194 DEG C, 195 DEG C,
196 DEG C, 197 DEG C, 198 DEG C, 199 DEG C, 200 DEG C, 201 DEG C, 202 DEG C, 203 DEG C, 204 DEG C, 205 DEG C or 206 DEG C, 207 DEG C, 208
DEG C, 209 DEG C or 210 DEG C.
Preferably, the reaction time is 22-48h, more preferably 24-30h.
Reaction time it is typical but non-limiting be, for example, 22h, 23h, for 24 hours, 25h, 26h, 27h, 28h, 29h, 30h,
31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h or 48h.
The present invention reacts under the conditions of reaction temperature is 190-210 DEG C, and carboxyl is coordinated with multiple tooth type, is easily formed
Multidimensional structure, gallium metal organic framework material obtained have preferable chemical stability and ratio of briquetting.
Below with reference to specific embodiment, comparative example and attached drawing, the present invention will be further described.
Embodiment 1
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent, includes the following steps；
(a) 20mg gallium metal organic framework material is taken to be dispersed in 25ml deionized water and 5ml dimethyl formamide solution,
And ultrasonic disperse 10 minutes, the suspension of gallium metal organic framework material is obtained, and detect fluorescence signal intensity；
(b) compound concentration is the standard solution of the repefral of 300ppm, by repefral
Standard solution titrates the suspension of gallium metal organic framework material, the titration volumes of each rutgers solution
For 70 μ L, the variation of fluorescence intensity, as shown in Figure 1.
The preparation method of the gallium metal organic framework material, comprising the following steps:
3.5 mMs of organic ligand pyromellitic acids, 7 mMs of gallium nitrate hydrates, 10mL deionized water are added to
In 50mL PPL material bottle and ultrasound is uniformly mixed it, puts it into 50rpm/min reaction 12 in shaking table after tightening bottle cap
Hour, it is subsequently placed in 200 DEG C of baking oven and reacts 24 hours, naturally cool to room temperature, be washed with deionized 3 times, natural air drying
Again with methanol is washed 3 times afterwards, is dried in vacuo 12 hours at 100 DEG C, is obtained gallium metal organic framework material.
Embodiment 2
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent, includes the following steps；
(a) 20mg gallium metal organic framework material is taken to be dispersed in 25ml deionized water and 5ml dimethyl formamide solution,
And ultrasonic disperse 8 minutes, the suspension of gallium metal organic framework material is obtained, and detect fluorescence signal intensity；
(b) compound concentration is the standard solution of the diethyl phthalate of 300ppm, by diethyl phthalate
Standard solution titrates the suspension of gallium metal organic framework material, and the titration volumes of diethyl phthalate solution are
70 μ L, the variation of fluorescence intensity, as shown in Figure 2.
The preparation method of the gallium metal organic framework material, comprising the following steps:
4 mMs of organic ligand pyromellitic acids, 8 mMs of gallium sulfate hydrates, 11.7mL deionized water are added to
In 50mLPPL material bottle and ultrasound is uniformly mixed it, tightens after bottle cap static 12 hours, is subsequently placed in 190 DEG C of baking oven
Reaction 24 hours, naturally cools to room temperature, is washed with deionized 3 times, and again with methanol is washed 3 times after natural air drying, at 100 DEG C
Vacuum drying 6 hours, obtains gallium metal organic framework material.
Embodiment 3
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent, includes the following steps；
(a) 20mg gallium metal organic framework material is taken to be dispersed in 25ml deionized water and 5ml dimethyl formamide solution,
And ultrasonic disperse 12 minutes, the suspension of gallium metal organic framework material is obtained, and detect fluorescence signal intensity；
(b) compound concentration is the standard solution of the bisphenol-A of 300ppm, by the standard solution of bisphenol-A to the organic bone of gallium metal
The suspension of frame material is titrated, and the titration volumes of each bisphenol-A solution are 70 μ L, the variation of fluorescence intensity, such as Fig. 3
It is shown.
The preparation method of the gallium metal organic framework material, comprising the following steps:
3 mMs of organic ligand pyromellitic acids, 5.4 mMs of gallium sulfate hydrates, 8mL deionized water are added to
In 50mLPPL material bottle and ultrasound is uniformly mixed it, tightens after bottle cap static 12 hours, is subsequently placed in 210 DEG C of baking oven
Reaction 24 hours, naturally cools to room temperature, is washed with deionized 3 times, and again with methanol is washed 3 times after natural air drying, at 100 DEG C
Vacuum drying 6 hours, obtains gallium metal organic framework material.
Embodiment 4
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent, includes the following steps；
(a) 20mg gallium metal organic framework material is taken to be dispersed in 25ml deionized water and 5ml dimethyl formamide solution,
And ultrasonic disperse 10 minutes, the suspension of gallium metal organic framework material is obtained, and detect fluorescence signal intensity；
(b) compound concentration is the standard solution of the bisphenol b of 300ppm, by the standard solution of bisphenol b to the organic bone of gallium metal
The suspension of frame material is titrated, and the titration volumes of each bisphenol b solution are 50 μ L, the variation of fluorescence intensity, such as Fig. 4
It is shown.
The preparation method of the gallium metal organic framework material, comprising the following steps:
3 mMs of organic ligand pyromellitic acids, 4.5 mMs of gallium sulfate hydrates, 7.5mL deionized water are added to
In 50mLPPL material bottle and ultrasound is uniformly mixed it, tightens after bottle cap static 12 hours, is subsequently placed in 210 DEG C of baking oven
Reaction 24 hours, naturally cools to room temperature, is washed with deionized 3 times, and again with methanol is washed 3 times after natural air drying, at 100 DEG C
Vacuum drying 6 hours, obtains gallium metal organic framework material.
Embodiment 5
A kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent, includes the following steps；
(a) 20mg gallium metal organic framework material is taken to be dispersed in 25ml deionized water and 5ml dimethyl formamide solution,
And ultrasonic disperse 9 minutes, the suspension of gallium metal organic framework material is obtained, and detect fluorescence signal intensity；
(b) compound concentration is the standard solution of the Bisphenol F of 300ppm, by the standard solution of Bisphenol F to the organic bone of gallium metal
The suspension of frame material is titrated, and the titration volumes of each Bisphenol F solution are 70 μ L, the variation of fluorescence intensity, such as Fig. 5
It is shown.
The preparation method of the gallium metal organic framework material, comprising the following steps:
3.5 mMs of organic ligand pyromellitic acids, 7 mMs of gallium nitrate hydrates, 10mL deionized water are added to
In 50mLPPL material bottle and ultrasound is uniformly mixed it, tightens after bottle cap static 12 hours, is subsequently placed in 200 DEG C of baking oven
Reaction 24 hours, naturally cools to room temperature, is washed with deionized 3 times, and again with methanol is washed 3 times after natural air drying, at 100 DEG C
Vacuum drying 12 hours, obtains gallium metal organic framework material.
Embodiment 6
A kind of gallium metal organic framework material detection incretion interferent Application in Sensing, except being 300ppm's with concentration
The standard solution of bisphenol AF titrates the suspension of gallium metal organic framework material, the titration volumes of each bisphenol AF solution
Other than 50 μ L, other operating procedures are same as Example 1.Fluorescence intensity testing result is as shown in Figure 6.
Embodiment 7
The Application in Sensing of a kind of gallium metal organic framework material in detection incretion interferent, except being 300ppm with concentration
The standard solution of bisphenol S the suspension of gallium metal organic framework material is titrated, the titration volumes of each bisphenol S solution
Other than 10 μ L, other operating procedures are same as Example 1.Fluorescence intensity testing result is as shown in Figure 7.
Embodiment 8
The Application in Sensing of a kind of gallium metal organic framework material in detection incretion interferent, except being 300ppm with concentration
Bisphenol fluorene standard solution the suspension of gallium metal organic framework material is titrated other than, other operating procedures and implement
Example 1 is identical.Fluorescence intensity testing result is as shown in Figure 8.
Fig. 1 is that repefral of the present invention titrates gallium metal organic framework material solution fluorescence Strength Changes song
Line；It is respectively 0 μ L, 70 μ in the dripping quantity for the peak value corresponding repefral from top to bottom that wavelength is 300-350nm
L, 140 μ L, 210 μ L, 280 μ L and 350 μ L；In the peak value corresponding phthalic acid two from top to bottom that wavelength is 350-500nm
The dripping quantity of methyl esters is respectively 0 μ L, 70 μ L, 140 μ L, 210 μ L, 280 μ L and 350 μ L；
Fig. 2 is that diethyl phthalate of the present invention titrates gallium metal organic framework material solution fluorescence Strength Changes song
Line；It is respectively 0 μ L, 70 μ in the dripping quantity for the peak value corresponding diethyl phthalate from top to bottom that wavelength is 300-350nm
L, 140 μ L, 210 μ L, 280 μ L and 350 μ L；In the peak value corresponding phthalic acid two from top to bottom that wavelength is 350-500nm
The dripping quantity of ethyl ester is respectively 0 μ L, 70 μ L, 140 μ L, 210 μ L, 280 μ L and 350 μ L；
Fig. 3 is that bisphenol-A of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；It is in wavelength
The dripping quantity of the peak value of 300-350nm corresponding bisphenol-A from top to bottom be respectively 0 μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L,
250 μ L, 300 μ L and 350 μ L；It is respectively 0 μ in the dripping quantity for the peak value corresponding bisphenol-A from top to bottom that wavelength is 350-500nm
L, 50 μ L, 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L and 350 μ L；
Fig. 4 is that bisphenol b of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；It is in wavelength
The dripping quantity of the peak value of 300-350nm corresponding bisphenol b from top to bottom be respectively 0 μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L,
250 μ L, 300 μ L, 350 μ L, 400 μ L and 450 μ L；In the drop for the peak value corresponding bisphenol b from top to bottom that wavelength is 350-500nm
Dosage is respectively 0 μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L, 350 μ L, 400 μ L and 450 μ L；
Fig. 5 is that Bisphenol F of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；It is in wavelength
The dripping quantity of the peak value of 300-350nm corresponding Bisphenol F from top to bottom be respectively 0 μ L, 70 μ L, 140 μ L, 210 μ L, 280 μ L and
350μL；The dripping quantity for the peak value corresponding Bisphenol F from top to bottom that wavelength is 350-500nm be respectively 0 μ L, 70 μ L, 140 μ L,
210 μ L, 280 μ L and 350 μ L；
Fig. 6 is that bisphenol AF of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；It is in wavelength
The dripping quantity of the peak value of 300-350nm corresponding bisphenol AF from top to bottom be respectively 0 μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L,
250 μ L, 300 μ L and 350 μ L；It is respectively 0 in the dripping quantity for the peak value corresponding bisphenol AF from top to bottom that wavelength is 350-500nm
μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L and 350 μ L；
Fig. 7 is that bisphenol S of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；
It is respectively 0 μ L, 10 μ L, 20 μ in the dripping quantity for the peak value corresponding bisphenol S from top to bottom that wavelength is 300-350nm
L, 30 μ L, 40 μ L, 50 μ L, 60 μ L, 70 μ L and 80 μ L；In the peak value that wavelength is 350-500nm corresponding bisphenol S from top to bottom
Dripping quantity is respectively 0 μ L, 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L, 60 μ L, 70 μ L and 80 μ L；
Fig. 8 is that bisphenol fluorene of the present invention titrates gallium metal organic framework material solution fluorescence intensity variation curve；It is in wavelength
The dripping quantity of the peak value of 300-350nm corresponding bisphenol fluorene from top to bottom be respectively 0 μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L,
250 μ L, 300 μ L and 350 μ L；It is respectively 0 in the dripping quantity for the peak value corresponding bisphenol fluorene from top to bottom that wavelength is 350-500nm
μ L, 50 μ L, 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L and 350 μ L.
Incretion interferent solution in Fig. 1, Fig. 2, Fig. 7 and Fig. 8 titrates gallium metal organic framework material solution, in wavelength
There is peak-fall twice for 300-500nm, i.e., in the peak value that wavelength is 300-350nm, as incretion interferent solution drips
Quantitative increase, fluorescence intensity gradually decrease, and a peak-fall occur；In the peak value that wavelength is 350-500nm, with interior point
The increase of chaff interferent solution titer is secreted, fluorescence intensity gradually decreases, and a peak-fall occurs.It follows that gallium metal
Organic framework material dimethyl terephthalate, diethyl phthalate, bisphenol S and bisphenol fluorene have good sensing energy
Power can be detected sensitively and obtain accurate detection result.
In Fig. 3, figure, 4 figures, 5 and Fig. 6, it is that 350-500nm a peak-fall occurs in wavelength, i.e., is in wavelength
350-500nm, with the increase of incretion interferent solution titer, fluorescence intensity is gradually decreased, and is 300-350nm in wavelength
There is minor peaks rising, i.e., with the increase of incretion interferent solution titer, fluorescence intensity is gradually increased.Thus may be used
Know, gallium metal organic framework material has extraordinary sensing capability to bisphenol-A, bisphenol b, Bisphenol F and bisphenol AF, and gallium metal has
Machine framework material can sensitively detect bisphenol-A, bisphenol b, Bisphenol F and bisphenol AF and accurate detection knot can be obtained
Fruit.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of Application in Sensing of gallium metal organic framework material in detection incretion interferent.
2. a kind of sensing of the gallium metal organic framework material according to claim 1 in detection incretion interferent is answered
Repefral, diethyl phthalate, bisphenol-A, double is selected from, which is characterized in that the incretion interferent
At least one of phenol B, Bisphenol F, bisphenol AF, bisphenol S and bisphenol fluorene.
3. Application in Sensing of the gallium metal organic framework material according to claim 1 in detection incretion interferent,
It is characterized in that, the gallium metal organic framework material is prepared by pyromellitic acid, trivalent gallium compound and water.
4. Application in Sensing of the gallium metal organic framework material according to claim 3 in detection incretion interferent,
It is characterized in that, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-4:6-8:450-650.
5. Application in Sensing of the gallium metal organic framework material according to claim 3 in detection incretion interferent,
It is characterized in that, the molar ratio of the pyromellitic acid, the trivalent gallium compound and the water is 3-3.5:7-7.5:500-560.
6. Application in Sensing of the gallium metal organic framework material according to claim 3 in detection incretion interferent,
It is characterized in that, the trivalent gallium compound is selected from one of gallium nitrate or gallium sulfate.
7. according to sensing of the described in any item gallium metal organic framework materials of claim 3-6 in detection incretion interferent
Using, which is characterized in that the gallium metal organic framework material preparation method the following steps are included:
Pyromellitic acid, trivalent gallium compound and water are mixed and reacted, gallium metal organic framework material is obtained.
8. Application in Sensing of the gallium metal organic framework material according to claim 7 in detection incretion interferent,
It is characterized in that, the temperature of the reaction is 190-210 DEG C, more preferably 195-205 DEG C.
9. Application in Sensing of the gallium metal organic framework material according to claim 7 in detection incretion interferent,
It is characterized in that, the reaction time is 22-48h.
10. Application in Sensing of the gallium metal organic framework material according to claim 7 in detection incretion interferent,
It is characterized in that the reaction time is 24-30h.
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