CN105758829A - Preparation method of nano composite for quickly detecting fluorine ions in water phase - Google Patents
Preparation method of nano composite for quickly detecting fluorine ions in water phase Download PDFInfo
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- CN105758829A CN105758829A CN201510807540.5A CN201510807540A CN105758829A CN 105758829 A CN105758829 A CN 105758829A CN 201510807540 A CN201510807540 A CN 201510807540A CN 105758829 A CN105758829 A CN 105758829A
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- nano composite
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Abstract
The invention discloses a preparation method of a nano composite for quickly detecting fluorine ions in a water phase.Prepared trimesoyl hydrazine salicylaldehyde derivative-attapulgite nano composite is capable of anchoring probe molecules having fluorine ion recognizing function to a hydrophilic nanorod matrix, thereby detecting fluorine ions in the water phase.Compared with the pure use of organic probe molecules, the nano composite of the invention is capable of selectively quickly detecting fluorine in a water resource and may be imparted sensitiveness through detection via naked eyes; in addition, as the nano composite is of natural attapulgite low in cost and has the surface anchored few probe molecules having fluorine ion recognizing function, the cost of the whole nano composite is greatly reduced.
Description
Technical field
The present invention relates to the preparation method of the nano composite material of fluorion in a kind of quick detection aqueous phase.
Background technology
Fluorine element is the trace element of needed by human, but works as Oil repellent in the drinking water in people's daily life and exceed
Will be detrimental to health during 4ppm and even cause the generation of intoxicating phenomenon.Such as, dental fluorosis and skeleton fluorosis are different
Country is found, and reason is just because fluorine excess in daily drunk water.The most also have been reported that the fluorine of display picked-up excess can be led
Cause the generation of osteosarcoma disease, if after child on long-term drinks the water of fluorine excess, the growth of brain can be injured thus induces intelligence
Problem.Thus quickly whether content of fluoride ion exceeds standard and is just particularly important in detection water source.In the past few decades, people
Devise and much there is the probe molecule identifying fluorion function.In the method for existing detection fluorion, majority be based on
Fluorion and the specific bond of probe molecule, such as hydrogen bond action, Lewis Acids and Bases effect etc..SuningWang et al. designs synthesis
A series of probe molecules, they have good selectivity and susceptiveness (less than 1 × 10 to fluorion-5M), but its shortcoming
It is exactly in non-polar solven, just can have good ion selectivity, thus limits its direct inspection in water source
Survey.Jong Seung Kim et al. also relates to a series of probe molecule with Fluoride recognition characteristic, although it has relatively
Good identity, but it is still its identity of competence exertion in general polar solvent.Nanometer of the present invention is multiple
Condensation material can be anchored at having the probe molecule identifying fluorion function in hydrophilic nano rod substrate, to realize it at water
Detection to fluorion in mutually.
Summary of the invention
The invention aims to provide and quickly detect the preparation method of the nano composite material of fluorion in aqueous phase.
For reaching above-mentioned purpose, the present invention implements according to techniques below scheme:
The preparation method of the nano composite material of fluorion in a kind of quick detection aqueous phase, comprises the following steps:
1) preparation has the probe molecule identifying fluorion function: by trimesic acid, concentrated sulphuric acid and ethanol according to 1:
The mass ratio of 0.25:20 dissolves in ethanol, after backflow 48h, obtain white product trimesic acid ethyl ester (1H NMR
(CDCl3):δH1.45 (t, 9H), 4.43 (m, 6H), 8.86 (s, 3H)；Elemental analysis:calcd for
C15H18O6: C 61.22%, H 6.16%, O 32.62%；Found:C 61.35%, H 6.31%, O 32.55%；White is solid
Body, productivity 95.27%)；Trimesic acid ethyl ester, hydrazine hydrate and methanol are dissolved in methanol with the mass ratio of 1:0.5:5,
During until there is no the point of raw material on lamellae, cooling reactant liquor to room temperature, separate out a large amount of white solid equal benzene three formylhydrazine (1H
NMR(d6-DMSO):δH3.26 (m, 6H), 7.85 (t, 3H), 10.85 (s, 3H)；Elemental analysis:calcd for
C9H12N6O3: C 42.86%, H 4.81%, O19.03%；Found:C 42.99%, H 4.66%, O 19.26%；White is solid
Body, productivity 91.28%)；Equal benzene three formylhydrazine and salicylaldehyde derivatives are dissolved in proper amount of methanol with the mol ratio of 1:4.5,
Add p-methyl benzenesulfonic acid and make catalyst, be cooled to after backflow 12h room temperature obtain fluorescent probe molecule (1H NMR(d6-DMSO):δH
(3.81 m, 9H), 6.95 (t, 6H), 7.38 (t, 3H), 7.72 (d, 3H), 8.82 (t, 6H), 11.26 (s, 3H), 12.58 (s,
3H)；Elemental analysis:calcd for C36H30N6O12: C 58.54%, H4.09%, O 25.99%；Found:
C 58.68%, H 4.22%, O 25.81%；White solid, productivity 96.53%), its reaction equation is as follows:
2) hydrophilic nano attapulgite is prepared: by the natural attapulgite of acidified process, the acetic acid of catalytic amount, ring
PEI (Polyetherimide) solution of ethyliminum and excess is centrifuged collection after stirring 24h in DMF (dimethylformamide) and obtains parent
Water nano substrate, reaction equation is as follows:
3) it is anchored at having the probe molecule identifying fluorion function in hydrophilic nano attapulgite substrate: by hydrophilic
Property nano-attapulgite stone and preparation have identify fluorion function probe molecule join ethanol and DMF with the mol ratio of 1:1
In the mixed solvent of (dimethylformamide), it is multiple that backflow 12h obtains equal benzene front three hydrazide salicylaldehyde derivant-palygorskite nano
Condensation material i.e. finished product, reaction equation is as follows:
Further, described step 1) in the 1-that addition is reactant equal benzene three formylhydrazine material amount of p-methyl benzenesulfonic acid
2%.
As preferably, described step 2) molecular weight of polymine needs at 100000-500000, polyethylenimine solution
To stir with rotor agitator at 40 DEG C.
Compared with prior art, in the quickly detection aqueous phase that prepared by the present invention, the nano composite material of fluorion is possible not only to
Fluorine element in selective quickly detection water source, and its sensitivity can be realized by open hole detection；In addition, because of
Being natural attapulgite for nano material described in this patent, it is with low cost, and its surface has simply anchored a small amount of has identification
The probe molecule of fluorion function, so greatly reduces the cost of whole nano composite material.
Accompanying drawing explanation
Fig. 1 be the nano composite material of the present invention aqueous solution in be sequentially added into the comparison figure that corresponding anion is later；
Fig. 2 be the nano composite material of the present invention aqueous solution in be sequentially added into the later ultraviolet of corresponding anion-can
See abosrption spectrogram；
In figure: a is pure water solution；B-e is for being separately added into different amounts of F-Aqueous solution；F-h is for adding Cl respectively-、Br-
And I-Aqueous solution.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described, the illustrative examples invented at this
And explanation is used for explaining the present invention, but not as a limitation of the invention.
Preparation has the probe molecule identifying fluorion function: by trimesic acid, concentrated sulphuric acid and ethanol according to 1:0.25:
The mass ratio of 20 dissolves in ethanol, after backflow 48h, obtain white product trimesic acid ethyl ester (1H NMR(CDCl3):δH
1.45 (t, 9H), 4.43 (m, 6H), 8.86 (s, 3H)；Elemental analysis:calcd for C15H18O6:C
61.22%, H 6.16%, O 32.62%；Found:C 61.35%, H 6.31%, O 32.55%；White solid, productivity
95.27%)；Trimesic acid ethyl ester, hydrazine hydrate and methanol are dissolved in methanol with the mass ratio of 1:0.5:5, until thin
When there is no the point of raw material on laminate, cooling reactant liquor to room temperature, separate out a large amount of white solid equal benzene three formylhydrazine (1H NMR(d6-
DMSO):δH3.26 (m, 6H), 7.85 (t, 3H), 10.85 (s, 3H)；Elemental analysis:calcd for
C9H12N6O3: C 42.86%, H 4.81%, O 19.03%；Found:C 42.99%, H 4.66%, O 19.26%；White
Solid, productivity 91.28%)；Equal benzene three formylhydrazine and salicylaldehyde derivatives are dissolved in proper amount of methanol with the mol ratio of 1:4.5
In, add p-methyl benzenesulfonic acid and make catalyst, be cooled to after backflow 12h room temperature obtain fluorescent probe molecule (1H NMR(d6-DMSO):
δH3.81 (m, 9H), 6.95 (t, 6H), 7.38 (t, 3H), 7.72 (d, 3H), 8.82 (t, 6H), 11.26 (s, 3H), 12.58
(s,3H)；Elemental analysis:calcd for C36H30N6O12: C 58.54%, H 4.09%, O 25.99%；
Found:C 58.68%, H 4.22%, O 25.81%；White solid, productivity 96.53%), its reaction equation is as follows:
Prepare hydrophilic nano attapulgite: by the natural attapulgite of acidified process, the acetic acid of catalytic amount, ring second
PEI (Polyetherimide) solution of imines and excess is centrifuged collection after stirring 24h in DMF (dimethylformamide) and obtains hydrophilic
Property nanomatrix, reaction equation is as follows:
It is anchored at having the probe molecule identifying fluorion function in hydrophilic nano attapulgite substrate: by hydrophilic
Nano-attapulgite stone and preparation have the probe molecule of identification fluorion function and join ethanol and DMF (two with the mol ratio of 1:1
Methylformamide) mixed solvent in, backflow 12h obtain equal benzene front three hydrazide salicylaldehyde derivant-palygorskite nano be combined
Material i.e. finished product, reaction equation is as follows:
Further, described step 1) in the 1-that addition is reactant equal benzene three formylhydrazine material amount of p-methyl benzenesulfonic acid
2%.
As preferably, described step 2) molecular weight of polymine needs at 100000-500000, polyethylenimine solution
To stir with rotor agitator at 40 DEG C.
Such as Fig. 1, use fluorion in the nano composite material detection aqueous solution of the present invention, pipette 1mL equal benzene three formylhydrazine
1mg × the mL of salicylaldehyde derivatives-palygorskite nano composite material-1Aqueous solution in a series of 10mL bottle a, b, c, d, e, f,
In g, h, b, c, d, e are sequentially added into 1mL, 2ml, 3ml, 4ml F-The 0.5mg × mL of 4-butyl ammonium-1In aqueous solution, no
Commensurability is separately added into 1mL F-, f, g, h are separately added into the Cl of 1mL-, Br-, I-The 0.5mg × mL of 4-butyl ammonium-1Water
In solution, and water-soluble liquid measure keeps consistent in making every bottle, observes dim light of night change, if as it is shown in figure 1, color becomes after mix homogeneously
Yellow then proves F-solution.
Such as Fig. 2, pipette the 1mg × mL of 1mL equal benzene front three hydrazide salicylaldehyde derivant-palygorskite nano composite material-1
Aqueous solution, in a series of 10mL bottle a, b, c, d, e, f, g, h, is sequentially added into 1mL, 2ml, 3ml, 4ml F in b, c, d, e-'s
0.5mg × the mL of 4-butyl ammonium-1In aqueous solution, different amounts of it is separately added into 1mL F-, f, g, h are separately added into 1mL's
Cl-, Br-, I-The 0.5mg × mL of 4-butyl ammonium-1In aqueous solution, and water-soluble liquid measure keeps consistent in making every bottle, mix homogeneously
After at 25 DEG C, survey its uv-visible absorption spectra, if it find that new stronger absworption peak occurs after 400nm, and
The absworption peak of about 340nm has substantially reduction, then be F-Solution.
Technical scheme is not limited to the restriction of above-mentioned specific embodiment, every does according to technical scheme
The technology deformation gone out, within each falling within protection scope of the present invention.
Claims (3)
1. the preparation method of the nano composite material of fluorion in a quick detection aqueous phase, it is characterised in that: include following step
Rapid:
1) preparation has the probe molecule identifying fluorion function: by trimesic acid, concentrated sulphuric acid and ethanol according to 1:0.25:20
Mass ratio dissolve in ethanol, backflow 48h after, obtain white product trimesic acid ethyl ester；By trimesic acid ethyl ester,
Hydrazine hydrate and methanol are dissolved in methanol with the mass ratio of 1:0.5:5, and during until not having the point of raw material on lamellae, cooling is anti-
Answer liquid to room temperature, separate out a large amount of white solid equal benzene three formylhydrazine；By equal benzene three formylhydrazine and salicylaldehyde derivatives with 1:4.5's
Mol ratio is dissolved in proper amount of methanol, adds p-methyl benzenesulfonic acid and makees catalyst, is cooled to room temperature and obtains fluorescent probe after backflow 12h
Molecule, its reaction equation is as follows:
2) hydrophilic nano attapulgite is prepared: by the natural attapulgite of acidified process, the acetic acid of catalytic amount, ring second Asia
PEI (Polyetherimide) solution of amine and excess is centrifuged collection after stir 24h in DMF dimethylformamide and obtains hydrophilic and receive
Mesityl matter, reaction equation is as follows:
3) it is anchored at having the probe molecule identifying fluorion function in hydrophilic nano attapulgite substrate: hydrophilic is received
Rice attapulgite and preparation have the probe molecule of identification fluorion function and join ethanol and DMF (diformazan with the mol ratio of 1:1
Base Methanamide) mixed solvent in, backflow 12h obtain equal benzene front three hydrazide salicylaldehyde derivant-palygorskite nano composite wood
Material i.e. finished product, reaction equation is as follows:
。
The preparation method of the nano composite material of fluorion, its feature in quick detection aqueous phase the most according to claim 1
Be: described step 1) in the 1-2% that addition is reactant equal benzene three formylhydrazine material amount of p-methyl benzenesulfonic acid.
The preparation method of the nano composite material of fluorion, its feature in quick detection aqueous phase the most according to claim 1
It being: described step 2) molecular weight of polymine is at 100000-500000, and polyethylenimine solution needs at 40 DEG C with turning
Sub-agitator stirs.
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Cited By (3)
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| CN108503598A (en) * | 2018-01-23 | 2018-09-07 | 天津大学 | Supermolecular gel compound and synthetic method and the application in fluorine ion detection |
| CN110204734A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of polyethyleneimine/salicylide modified cellulosic materials and its preparation method and application |
| CN114214059A (en) * | 2021-11-18 | 2022-03-22 | 淮阴工学院 | Fluorine ion fluorescent probe and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204734A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of polyethyleneimine/salicylide modified cellulosic materials and its preparation method and application |
| CN110204734B (en) * | 2019-06-14 | 2021-10-01 | 陕西科技大学 | Polyethyleneimine/salicylaldehyde modified cellulose material and preparation method and application thereof |
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| CN114214059B (en) * | 2021-11-18 | 2024-03-12 | 淮阴工学院 | Fluorine ion fluorescent probe and preparation method and application thereof |
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