CN103343000A - Metal ion parallel detection material based on porous silica and preparation method and application thereof - Google Patents
Metal ion parallel detection material based on porous silica and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal ion parallel detection material based on porous silica and a preparation method thereof. According to the material, porous silica serves as a carrier, azide amino group and amino group are respectively modified on the inner wall of the pore channel and the outer surface of the porous silica; a first metal ion fluorescence probe molecule is in covalent connection with the azide amino group; a second metal ion fluorescence probe molecule is in covalent connection with the amino group. By utilizing the design of ingenious preparation route, distribution of different metal ion fluorescence probe molecules on the carrier is accurately controlled, and effective space separation is realized; and the material is high in stability and excellent in dispersing performance, parallel detection of multiple metal ions can be performed in water or an organic solvent according to the needs, and the metal ion parallel detection material is high in selectivity, high in sensitivity and high in interference resistance.
Description
Technical field
The present invention relates to heavy metal ion fluoroscopic examination field, a kind of two metal ion species parallel detection materials based on porous silica particularly, and the preparation method of this test material and application.
Background technology
In recent years all over the world particularly developing country's heavy metal pollution problem highlight day by day, China in 2011 only " blood lead " event has just taken place tens of, serious cadmium pollution event has taken place again in Longjiang, Guangxi during the Spring Festival in 2012, has caused abominable social influence.Because heavy metal ion has the characteristic of biomagnification, difficult degradation generally can not excrete by the pathways metabolism of organism self, causes very easily that human body is poisoned to cause a series of pathologies (carcinogenic, cause disease, mutagenesis).
The heavy metal contamination present situation belongs to combined type to be polluted, and with the variation of region, the industrial structure difference to some extent.Not long ago, China different cities soil sample survey result shows, in, eastern region lead, mercury, cadmium pollution situation is comparatively obvious, western part then copper, nickel, zinc pollution is comparatively serious, there is in various degree pollution in south, the west and south then heavy metals such as copper, lead, zinc, cadmium.Therefore, the exploitation highly sensitive develops heavy metal detection architecture (the non-interfering parallel detection of polycomponent etc.) easily, and the environmental compatibility of expanding test material simultaneously is the emphasis of studying at present with functional (detect performance can free composite design).
Since reported first fluorescent probe methods such as Tsien in 1980 can sensitive detection metal ion, this means selectivity characteristic good, highly sensitive, that detect real-time high-efficiency has promptly obtained investigator's approval, and becomes one of important way of heavy metal ion detection gradually.Yet most of organic fluorescence probe molecules dissolution dispersity in water is relatively poor, and measuring ability is single, also has stability problem under complex conditions, is difficult to satisfy the detection demand under the various environment.If simple mixing of several different heavy metal fluorescent probe molecules detected, in most cases can be because of the coupling generation FRET (fluorescence resonance energy transfer) (FRET of spectral quality between the probe molecule, operating range ~ 10 nm), subtract the fluorescent emission intensity of hypofluorescence Give body, strengthen the fluorescent emission intensity of fluorescent receptor.And in contents of many kinds of heavy metal ion parallel detection process, the fluorescent emission of each probe molecule changes i.e. corresponding the change in concentration of corresponding heavy metal ion, and the FRET process will certainly influence Accurate Analysis and the detection of heavy metal ion.
Under the present situation that the heavy metal combined type is polluted, need a kind of scheme, multiple organic fluorescence probe can be assembled by efficient manner, be integrated in the detection architecture, satisfy the demand of contents of many kinds of heavy metal ion parallel detection.
Summary of the invention
In order to overcome existing heavy metal ion detection technique of fluorescence above shortcomings, the invention provides a kind of two metal ion species parallel detection materials based on porous silica and preparation method and the application of this test material; It modifies different functional groups at porous silica particle outside surface respectively with the duct inwall, utilize the reactive difference of these functional groups, and then finish the modification of different metal ion fluorescence probe molecule respectively at the duct of porous silica inwall and particle outside surface, to realize sensitivity, convenient, the non-interfering parallel fluoroscopic examination of different heavy metal ion efficiently.
Two metal ion species parallel detection materials based on porous silica of the present invention, it is characterized in that, this material is carrier with the porous silica, the duct inwall of described porous silica, outside surface are modified with folded amine groups and amino group respectively, the first metal ion species fluorescent probe molecule and described azido group are covalently bound, and the second metal ion species fluorescent probe molecule and described amino group are covalently bound.
Wherein, described porous silica is the ordered porous silicon oxide of MCM-41 type of monodisperse sphere shape.
The described first metal ion species fluorescent probe molecule has alkynyl group, and the described second metal ion species fluorescent probe molecule has carboxylic group.Can have the fluorescent probe independent assortment that carboxyl or alkynyl group also can detect different heavy metal ion as required, be used for common two metal ion species that detect, as the common detection of copper, mercury ion, the common detection of lead, mercury ion etc.
In the preferred embodiment, the described first metal ion species fluorescent probe molecule is the mercury ion fluorescent probe molecule that has alkynyl group, and the described second metal ion species fluorescent probe molecule is to be carboxy-modified copper ion fluorescence probe molecule.The structure of described mercury ion fluorescent probe molecule (probe 1), described copper ion fluorescence probe molecule (probe 2) is respectively suc as formula shown in I, the formula II:
A kind of mercury based on porous silica, cupric ion parallel detection preparation methods may further comprise the steps:
(1) preparation of .MCM-41 type porous silica
In containing the alkaline aqueous solution of ionogenic surfactant, successively slowly dripping volume ratio is 1 chloropropyl triethoxysilane and tetraethoxysilane (TEOS than 8-12, ~ 15 min), and 80 ℃ of reactions 2 hours, filter, collect the gained precipitation, washing, vacuum-drying obtains MCM-41 type porous silica;
(2). the porous silica outside surface is modified amino group
The porous silica (not removing surfactant templates) that step (1) is obtained is dispersed in the toluene solution that is dissolved with the aminopropyl-triethoxy siloxanes coupling agent of this porous silica equivalent and reacts, with the reaction mixture centrifugation, obtain intermediate product M1; This intermediate product M1 is the porous silica that outside surface is modified with amino group;
(3). removal step (2) obtains the surfactant templates among the intermediate product M1, makes the cl radical of its duct inwall exposed;
(4). the nitrine of porous silica internal surface is functionalized
With N, dinethylformamide (DMF) is solvent, carries out azido reaction with sodiumazide with the intermediate product M1 that removes surfactant templates, change the cl radical of the duct inwall of described intermediate product M1 into azido group, after reaction finished, centrifugation obtained intermediate product M2; This intermediate product M2 is the porous silica that is modified with amino group and azido group;
(5). on the described intermediate product M2 basis that step (4) obtains, utilize the differential responses performance of amino group that the subregion modifies and azido group to realize the locator qualification of different heavy metal fluorescent probe molecules;
At first at cuprous bromide, 2, under 2 '-dipyridyl existence condition, utilize the click chemistry reaction to make described azido group and the mercury ion fluorescent probe molecule covalence graft that has alkynyl group; Then, utilize the acidylate condensation reaction to make described amino group and carboxy-modified copper ion fluorescence probe molecule covalence graft, after reaction finishes that reaction mixture is centrifugal, and with methyl alcohol repetitive scrubbing several, get described test material.
Among the above-mentioned preparation method, the described ionogenic surfactant of step (1) is cetyl trimethylammonium bromide (CTAB).
The described reaction of step (2) is to carry out under the nitrogen protection condition.
The removal of the surfactant templates among the described intermediate product M1 of step (3) is to realize in the methanol solution of hydrochloric acid.
The mass ratio of the intermediate product M1 of the described sodiumazide of step (4) and removal surfactant templates is 1:0.5-1.5.
The structure that step (5) is described to have the mercury ion fluorescent probe molecule of alkynyl group, a described carboxy-modified copper ion fluorescence probe molecule respectively suc as formula 1, shown in the formula 2:
In the step (5), described intermediate product M2 and the described mass ratio that has the mercury ion fluorescent probe molecule of alkynyl group are 1-4:1; Having modified the intermediate product M2 of mercury ion fluorescent probe and the mass ratio of carboxy-modified copper ion fluorescence probe molecule is 1-4:1.
Test material of the present invention is in the parallel application of measuring two metal ion species in water or the organic solvent environment, and this two metal ion species can be cupric ion and mercury ion; It is in 7.0 the PBS damping fluid that described test material is dispersed in the pH value, and adds in detecting solution gradually and contain cupric ion and mercury ion solution to be measured carries out fluorometric titration, waits for that carrying out fluorescence spectrum after 10 minutes tests.
The present invention is incorporated into two kinds of small molecules heavy metal ion fluorescent probes in the hydridization assembling carrier, utilize and prepare highway route design cleverly, make that the distribution of different fluorescent probe molecules on carrier is precisely controlled and realized effective space obstacle, can realize the collaborative detection of two metal ion species simultaneously.
This system can design the preparation test material according to the detection demand with detecting the fluorescent probe independent assortment of different heavy metal ion, is used for common two metal ion species that detect, as the common detection of copper, mercury ion, and the common detection of lead, mercury ion etc.Only corresponding probe molecule need be modified alkynyl respectively, carboxyl just can be tackled the demand of different testing environments.
Test material good stability of the present invention, dispersing property is excellent, can be according to need carrying out the detection of different metal ion in water or in the organic solvent, and selectivity is good, highly sensitive, strong interference immunity, and efficient.
Test material of the present invention can settle out from detect liquid under action of centrifugal force, can realize comparatively easily heavy metal ion enrichment and separate, and is simple and easy to do.
Test material of the present invention can be modified multiple matrix (test paper, chip, film etc.) by the sol-gel process in the preparation process and be gone up use, has important potential using value.
Description of drawings
Fig. 1, Fig. 2 be the used mercury ion fluorescent probe that has an alkynyl group among the embodiment, have the nuclear magnetic spectrum of the copper ion fluorescence probe of carboxylic group;
Fig. 3, Fig. 4, Fig. 5 are the high resolution transmission electron microscopy digital photographs that porous silica is modified two kinds of fluorescence molecules front and back;
Fig. 6 is that the thermal weight loss in porous silica duct inwall and the outside surface otherness modification characterizes;
Fig. 7 is the infrared spectra in porous silica duct inwall and the outside surface otherness modification;
Fig. 8, Fig. 9 are X-ray diffraction and the nitrogen adsorption desorption Experimental Characterization that porous silica duct inwall and outside surface have been modified two kinds of fluorescent probe molecule front and back;
Figure 10 is that two metal ion species fluorescent probe molecules are adding by the uv absorption spectra before and after the measured ion;
Figure 11, Figure 12 are test material fluoroscopic examination spectrograms to mercury, two kinds of ions of copper in the PBS damping fluid;
Figure 13, Figure 14 are test material detects cupric ion, mercury ion in the PBS damping fluid selectivity sign figure;
Figure 15 is a routine spherical MCM-41 type porous silica synoptic diagram (not removing surfactant templates);
Figure 16 is the synoptic diagram that an example is modified with the porous silica of amino group and azido group;
Figure 17 is the synoptic diagram of a routine mercury, cupric ion parallel detection material.
Embodiment
Below in conjunction with specific embodiment the present invention is described in detail.
Exemplary embodiments: prepare a kind of mercury based on porous silica, cupric ion parallel detection material.
Carrier adopts the ordered porous silicon oxide of MCM-41 type of monodisperse sphere shape, with reference to Fig. 3,4, and this porous silica, specific surface area is big, and the site of controlled chemically modified is many, good stability, and form, big I are regulated with the need, and its outside surface and duct inwall all can carry out functional chemically modified.The metal-ion fluorescent probe molecule adopts and has the mercury ion fluorescent probe molecule of alkynyl group and carboxy-modified copper ion fluorescence probe molecule, respectively shown in formula I as mentioned in the above, the formula II.
Preparation process is as follows:
(1). the preparation of MCM-41 type porous silica
At first 1.0 g ionogenic surfactant Trimethyllaurylammonium bromides (CTAB) are dissolved in the 480 mL ultrapure waters, (NaOH 2M), and is preheated to 80 ℃ with the aqueous solution to add the aqueous solution of 3.5 mL sodium hydroxide.Under mechanical stirring, in reaction system, drip 0.5 mL chloropropyl triethoxysilane lentamente by dropping funnel, and then Dropwise 5 .0 mL tetraethoxysilane (TEOS, ~ 15 min), reaction mixture is continued reaction 2 hours down at 80 ℃, and be cooled to room temperature after the question response end.Filter, collect the precipitation of separating out in the process of cooling, successively use ultrapure water and methyl alcohol repetitive scrubbing.The gained filter cake is put into the vacuum drying oven dried overnight, and obtaining the white powder product is MCM-41 type porous silica; Figure 15 is spherical this porous silica synoptic diagram (not removing surfactant templates) of an example.
(2). the preparation of the amido modified porous silica of outside surface
Porous silica 2 g that step (1) is made are scattered in the 200mL toluene solution, and add aminopropyl-triethoxy siloxanes coupling agent 2.0 g (9 mmol); Under the protection of nitrogen atmosphere, reaction system is heated to backflow, and reaction is spent the night.Reaction with the reaction mixture centrifugation purifying of gained, and is used methanol wash, repeatedly with products therefrom vacuum-drying after finishing.
(3). the removal of surfactant templates
With amido modified porous silica 1.5 g of the outside surface of step (2) gained, be distributed in the hydrochloric methanol solution that is mixed with by 30 mL concentrated hydrochloric acids (37 wt %) and 210 mL methyl alcohol, under magnetic agitation, keep refluxing and spend the night; In this operating process, the surfactant templates in this porous silica hole can be removed, and inwall manifests cl radical.The porous silica of having removed tensio-active agent is successively used ultrapure water and methyl alcohol repetitive scrubbing, and in vacuum drying oven dried overnight.
(4). the nitrine of porous silica internal surface is functionalized
With the removal of step (2) gained the amido modified porous silica 1g of outside surface of surfactant templates, be scattered in the N of 100 mL, in the dinethylformamide (DMF), in reaction system, add the 1g sodiumazide then; The gained mixing solutions is heated to 100 ℃, and under this temperature, reacted 48 hours.After reaction finishes, reaction mixture is centrifugal, and with ultrapure water and methyl alcohol repetitive scrubbing several, the product vacuum-drying of gained is spent the night, namely get the porous silica (i.e. intermediate product M2 above) that is modified with amino group and azido group; With reference to Figure 16 one this porous silica synoptic diagram of example.
(5). utilize the azido group of the porous silica duct inwall modification of step (4) gained, the amino group of outside surface modification to realize the locator qualification of different heavy metal fluorescent probe molecules;
In 100 mL, three neck round-bottomed flasks, the intermediate product M2 of 0.7 g step (4) gained is scattered among the 50 mL DMF, and adds the mercury ion fluorescent probe of 400 mg band alkynyl; The gained reaction mixture was removed oxygen 1 hour under normal temperature high pure nitrogen stream condition, and under nitrogen protection, add part 2 successively, 2 '-dipyridyl (312 mg, 2.0 mmol) and catalyzer cuprous bromide (143 mg, 1.0 mmol); Reaction mixture is warming up to 60 ℃, and under the nitrogen protection condition, reacted 8 hours; The question response mixture is cooled to room temperature, uses methyl alcohol, ethylenediamine tetraacetic acid (EDTA) (EDTA) aqueous solution (10 mM), distilled water wash successively for several times, and centrifugation;
After this intermediate product M2 modified the mercury ion fluorescent probe molecule, modify subsequently cupric ion is had the fluorescent probe that selectivity detects.In 100 mL single necked round bottom flask, copper ion fluorescence probe molecule 300 mg that will have carboxyl are dissolved in 30 mL tetrahydrofuran (THF)s (THF), and adding condensing agent N, N '-dicyclohexylcarbodiimide (0.206 g, 1 mmol), (12 mg 0.1mmol) activate half an hour to the 4-Dimethylamino pyridine; Then, intermediate product M2 0.5 g that has modified the mercury ion fluorescent probe is distributed in the reaction mixture normal-temperature reaction 24 hours.After reaction finishes, reaction mixture is centrifugal, and with the methyl alcohol repetitive scrubbing for several times; Product dried overnight in vacuum drying oven with gained, namely obtain above-mentioned mercury, cupric ion parallel detection material, electron photomicrograph is seen Fig. 5, Figure 17 is the synoptic diagram of a routine mercury, cupric ion parallel detection material, and the surfaces externally and internally of porous silica is modified with mercury ion fluorescent probe molecule (probe 1), copper ion fluorescence probe molecule (probe 2) respectively.
A kind of mercury based on porous silica of method for preparing, cupric ion parallel detection material
,The ordered porous silicon oxide of MCM-41 type with the monodisperse sphere shape is carrier, the duct inwall of described porous silica, outside surface are modified with folded amine groups and amino group respectively, the mercury ion fluorescent probe molecule and the described azido group that have alkynyl group are covalently bound, and carboxy-modified copper ion fluorescence probe molecule and described amino group are covalently bound.
The application of above-mentioned test material parallel detection different metal ion, this mercury, cupric ion parallel detection material (as 1 mg) are dispersed in the 20 mL PBS damping fluids (pH 7.0), and in detecting solution, add gradually and contain mercury ion or cupric ion solution to be measured carries out fluorometric titration, waits for that carrying out fluorescence spectrum after 10 minutes tests.The solution to be measured of mercury, cupric ion is the aqueous solution or organic mixing solutions.
Below in conjunction with accompanying drawing this test material and detected result are described further.
The mercury ion that test material of the present invention is used, the nuclear magnetic spectrum of copper ion fluorescence probe molecule are seen Fig. 1,2, Fig. 1 is the nuclear magnetic spectrum of used alkynyl-modified mercury ion fluorescent probe among the embodiment, and Fig. 2 is the nuclear magnetic spectrum of the copper ion fluorescence probe of carboxyl modified among the embodiment.
Fig. 3, Fig. 4, Fig. 5 are the high resolution transmission electron microscopy digital photographs that porous silica is modified two kinds of fluorescence molecules front and back; Fig. 3 represents nanoporous silicon oxide form, the form behind Fig. 4 presentation graphs 3 local amplifications.Fig. 5 represents to modify the porous nano silicon oxide form of organic fluorescent probe, can clearly see the organism thin layer that contrast is low slightly at the skin of inorganic porous silicon oxide, proves that fluorescent probe molecule is modified successfully on the porous silica.
Fig. 6 is thermal weight loss (TGA) collection of illustrative plates in porous silica duct inwall and the outside surface otherness modification, wherein, (a) porous silica, (b) amino group and azido group locator qualification porous silica, (c) fluorescent probe molecule is modified porous silica.
Fig. 7 is the infrared spectra in porous silica duct inwall and the outside surface otherness modification, wherein, (a) porous silica, (b) amino group and azido group locator qualification porous silica, (c) fluorescent probe molecule is modified porous silica.
Fig. 8, Fig. 9 are X-ray diffraction (XRD) and the nitrogen adsorption desorption Experimental Characterization that the porous silica inside and outside wall has been modified two kinds of fluorescence molecule front and back.The XRD characterization result shows, porous silica after having modified two kinds of probe molecules, its 110,200, and the diffraction peak at 210 places significantly diminishes; Simultaneously, in the nitrogen adsorption experiment, measured isothermal absorption curve is trended towards changing to the I type of common non-porous material by the IV type of vesicular material property, has proved that also porous silica successfully modifies organic probe molecule.
To be two metal ion species fluorescent probe molecules adding by the uv absorption spectra before and after the measured ion Figure 10, wherein a), b) be the copper ion fluorescence probe that has carboxyl, c), d) be the mercury ion fluorescent probe that has alkynyl.According to the diagram result, mercury ion probe excitation wavelength is chosen as 390nm, and this wavelength can not excite copper ion probe to produce fluorescence; Same, the copper ion probe excitation wavelength is chosen as 510nm, and this wavelength can not excite the mercury ion probe to produce fluorescence, and two testing processes can not disturbed mutually.
Figure 11, Figure 12 represent test material (pH7.0 in the PBS damping fluid, 0.05g/L) fluorescence intensity is with (A) mercury ion (λ ex=390 nm), (B) the fluorescence spectrum figure of cupric ion (λ ex=510 nm) change in concentration, the heavy metal concentration that the fluorescent probe molecule fluorescent emission intensity is changed 10% correspondence is defined as detectability, and wherein the detection of cupric ion is limited to 2 * 10
-7Mol/L, the detection of mercury ion is limited to 5 * 10
-8Mol/L.
Figure 13, Figure 14 are that (pH7.0 0.05g/L) detects mercury ion (λ ex=390 nm) to test material, and the selectivity of cupric ion (λ ex=510 nm) characterizes figure, removes Hg in the selectivity test in the PBS damping fluid
2+, Cu
2+, also have Na
+, K
+, Ag
+, Co
2+, Pb
2+, Ni
2+, Cd
2+, Fe
2+, Fe
3+, Zn
2+Deng positively charged ion, by this figure as can be seen two kinds of fluorescent probe molecules respectively mercury ion, cupric ion are had obvious selectivity.
More than by specific embodiment the present invention has been done detailed explanation, these concrete descriptions can not think that the present invention only only limits to the content of these embodiment.Those skilled in the art conceive according to the present invention, these descriptions and any improvement of making in conjunction with general knowledge known in this field, be equal to replacement scheme etc., all should be included in the protection domain of claim of the present invention.
Claims (10)
1. two metal ion species parallel detection materials based on porous silica, it is characterized in that, this material is carrier with the porous silica, the duct inwall of described porous silica, outside surface are modified with folded amine groups and amino group respectively, the first metal ion species fluorescent probe molecule and described azido group are covalently bound, and the second metal ion species fluorescent probe molecule and described amino group are covalently bound.
2. material as claimed in claim 1 is characterized in that, described porous silica is the ordered porous silicon oxide of MCM-41 type of monodisperse sphere shape.
3. material as claimed in claim 1 or 2 is characterized in that, the described first metal ion species fluorescent probe molecule has alkynyl group, and the described second metal ion species fluorescent probe molecule has carboxylic group.
4. material as claimed in claim 1 or 2, it is characterized in that, the described first metal ion species fluorescent probe molecule is the mercury ion fluorescent probe molecule that has alkynyl group, and the described second metal ion species fluorescent probe molecule is to be carboxy-modified copper ion fluorescence probe molecule.
5. material as claimed in claim 4 is characterized in that, the structure of described mercury ion fluorescent probe molecule, described copper ion fluorescence probe molecule is respectively suc as formula shown in I, the formula II,
6. the mercury based on porous silica, cupric ion parallel detection preparation methods is characterized in that, may further comprise the steps:
(1). in containing the alkaline aqueous solution of ionogenic surfactant, successively slowly dripping volume ratio is 1 chloropropyl triethoxysilane and tetraethoxysilane than 8-12, and 80 ℃ of reactions, filter, collect the gained precipitation, washing, vacuum-drying obtains MCM-41 type porous silica;
(2). the porous silica that step (1) is obtained is dispersed in the toluene solution that is dissolved with the aminopropyl-triethoxy siloxanes coupling agent of this porous silica equivalent and reacts, and with the reaction mixture centrifugation, obtains intermediate product M1; This intermediate product M1 is the porous silica that outside surface is modified with amino group;
(3). removal step (2) obtains the surfactant templates among the intermediate product M1, makes the cl radical of its duct inwall exposed;
(4). with N, dinethylformamide (DMF) is solvent, carries out azido reaction with sodiumazide and the intermediate product M1 that removes surfactant templates, changes the cl radical of the duct inwall of described intermediate product M1 into azido group, obtains intermediate product M2; This intermediate product M2 is the porous silica that is modified with amino group and azido group;
(5). utilize step (4) to obtain the amino group of intermediate product M2 subregion modification and the differential responses performance of azido group, at first at cuprous bromide, 2, under 2 '-dipyridyl existence condition, utilize the click chemistry reaction to make described azido group and the mercury ion fluorescent probe molecule covalence graft that has alkynyl group; Then, utilize the acidylate condensation reaction to make described amino group and carboxy-modified copper ion fluorescence probe molecule covalence graft, get described test material.
7. method as claimed in claim 6 is characterized in that, ionogenic surfactant described in the step (1) is cetyl trimethylammonium bromide (CTAB).
8. as claim 6 or 7 described methods, it is characterized in that,
In the step (2), described reaction is to carry out under the nitrogen protection condition;
In the step (3), the surfactant templates of removing among the described intermediate product M1 is to realize in the methanol solution of hydrochloric acid;
In the step (4), the mass ratio of the intermediate product M1 of described sodiumazide and removal surfactant templates is 1:0.5-1.5.
9. method as claimed in claim 6 is characterized in that, in the step (5), the structure of the described mercury ion fluorescent probe molecule that has an alkynyl group, described carboxy-modified copper ion fluorescence probe molecule is respectively suc as formula shown in I, the formula II,
10. the described test material of any one claim of claim 1-5 is in the parallel application of measuring two metal ion species in water or the organic solvent environment.
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| CN107312020A (en) * | 2017-06-05 | 2017-11-03 | 延安大学 | A kind of colorimetric and the double response type TNP detection probes of fluorescence and preparation method thereof |
| CN109706223A (en) * | 2019-01-04 | 2019-05-03 | 中国药科大学 | It is a kind of based on receiving the MicroRNA detection method of flow control |
| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105482812A (en) * | 2015-12-18 | 2016-04-13 | 贵州大学 | Fluorescent probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance |
| CN107312020A (en) * | 2017-06-05 | 2017-11-03 | 延安大学 | A kind of colorimetric and the double response type TNP detection probes of fluorescence and preparation method thereof |
| CN109706223A (en) * | 2019-01-04 | 2019-05-03 | 中国药科大学 | It is a kind of based on receiving the MicroRNA detection method of flow control |
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| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
| CN111285897B (en) * | 2020-03-03 | 2022-06-07 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
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