CN103343000B - 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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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000001514 detection method Methods 0.000 title claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000523 sample Substances 0.000 claims abstract description 56
- 125000003277 amino group Chemical group 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 37
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007850 fluorescent dye Substances 0.000 claims description 31
- 239000013067 intermediate product Substances 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 25
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910021426 porous silicon Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- -1 siloxanes Chemical class 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 17
- 238000010586 diagram Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000013016 damping Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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
Particularly developing country's heavy metal pollution problem highlights day by day all over the world in recent years, China in 2011 only " blood lead " event has just occurred tens of, having there is again serious cadmium pollution event in Longjiang, Spring Festival Guangxi in 2012, has caused severe social influence.Because heavy metal ion has the characteristic of biomagnification, difficult degradation, generally can not excrete by the pathways metabolism of organism self, very easily causes the poisoning a series of pathologies (carcinogenic, cause disease, mutagenesis) that cause of human body.
Heavy metal pollution state belongs to combined type and pollutes, and with the variation of region, the industrial structure difference to some extent.Not long ago, China's different cities soil sample survey result shows, in, eastern region lead, mercury, cadmium pollution situation is comparatively obvious, western part copper, nickel, zinc pollution is comparatively serious, there is pollution in various degree in south, the west and south heavy metal such as copper, lead, zinc, cadmium.Therefore, exploitation highly sensitive, develops heavy metal detection system (the non-interfering parallel detection of polycomponent etc.) easily, and the environmental compatibility of simultaneously expanding test material is the emphasis of studying at present with functional (detect performance can free composite design).
Since detection metal ion that can be sensitive from reported first fluorescent probe methods such as Tsien in 1980, this means selectivity characteristic good, highly sensitive, that detect real-time high-efficiency has promptly obtained investigator's approval, and becomes gradually one of important way of detection of heavy metal ion.Yet most of organic fluorescence probe molecules dissolution dispersity in water is poor, measuring ability is single, in complex condition existence and stability problem also, is difficult to meet the detection demand under 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 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, FRET process will certainly affect Accurate Analysis and the detection of heavy metal ion.
Under the present situation of polluting in heavy metal combined type, need a kind of scheme, multiple organic fluorescence probe can be assembled by efficient manner, be integrated in a detection system, meet 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 respectively different functional groups at porous oxidation silicon grain outside surface and duct inwall, utilize the reactive difference of these functional groups, and then at the duct of porous silica inwall and particle outside surface, complete respectively the modification of different metal ion fluorescence probe molecule, the non-interfering parallel fluoroscopic examination of sensitive to realize, convenient, efficient different heavy metal ion.
The two metal ion species parallel detection materials based on porous silica of the present invention, it is characterized in that, this material be take porous silica as carrier, duct inwall, the outside surface of described porous silica are modified with respectively azido group and amino group, the first metal-ion fluorescent probe molecule and described azido group are covalently bound, and the second metal-ion 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.
Described the first metal-ion fluorescent probe molecule has alkynyl group, and described the second metal-ion fluorescent probe molecule has carboxylic group.Can also can detect the fluorescent probe independent assortment of different heavy metal ion with carboxyl or alkynyl group as required, 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 preferred embodiment, described the first metal-ion fluorescent probe molecule is the mercury ion fluorescence probe molecule with alkynyl group, and described the second metal-ion fluorescent probe molecule is to be carboxy-modified copper ion fluorescence probe molecule.The structure of described mercury ion fluorescence probe molecule (probe 1), described copper ion fluorescence probe molecule (probe 2) is respectively suc as formula shown in I, formula II:
。
A preparation method for mercury based on porous silica, cupric ion parallel detection material, comprises the following steps:
(1) preparation of .MCM-41 type porous silica
In containing the alkaline aqueous solution of ionogenic surfactant, successively slowly drip volume ratio and be 1 than the chloropropyl triethoxysilane of 8-12 and tetraethoxysilane (TEOS, ~ 15 min), and 80 ℃ of reactions 2 hours, filter, collect gained precipitation, washing, vacuum-drying, obtains MCM-41 type porous silica;
(2). porous silica outside surface is modified amino group
The porous silica that step (1) is obtained (not removed surfactant templates) is dispersed in to be dissolved with the toluene solution of the aminopropyl-triethoxy siloxanes coupling agent of this porous silica equivalent and reacts, by reaction mixture centrifugation, obtain intermediate product M1; This intermediate product M1 is the porous silica that outside surface is modified with amino group;
(3). remove step (2) and obtain the surfactant templates in intermediate product M1, make the cl radical of its duct inwall exposed;
(4). the nitrine of porous silica internal surface is functionalized
The DMF (DMF) of take is solvent, with the intermediate product M1 of sodiumazide and removal surfactant templates, carries out azido reaction, change the cl radical of the duct inwall of described intermediate product M1 into azido group, after reaction finishes, centrifugation, obtains 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 of obtaining in step (4), utilize the amino group of subregion modification and the differential responses performance of azido group to realize the locator qualification of different heavy metal fluorescent probe molecules;
First at cuprous bromide, 2, under 2 '-dipyridyl existence condition, utilize click chemistry reaction to make described azido group and mercury ion fluorescence probe molecule covalence graft with alkynyl group; Then, utilize acidylate condensation reaction to make described amino group and carboxy-modified copper ion fluorescence probe molecule covalence graft, after reaction finishes, reaction mixture is centrifugal, and with methyl alcohol repetitive scrubbing several, obtain described test material.
In 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 nitrogen protection condition.
The removal of the surfactant templates in 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.
Step (5) described with the mercury ion fluorescence probe molecule of alkynyl group, the structure of described carboxy-modified copper ion fluorescence probe molecule respectively suc as formula 1, shown in formula 2:
。
In step (5), the mass ratio of described intermediate product M2 and the described mercury ion fluorescence probe molecule with alkynyl group is 1-4:1; Modified the intermediate product M2 of mercury ion fluorescence probe and the mass ratio of carboxy-modified copper ion fluorescence probe molecule is 1-4:1.
The application of two metal ion species of test material of the present invention in Parallel Determination water or organic solvent environment, this two metal ion species can be cupric ion and mercury ion; It is in 7.0 PBS damping fluid that described test material is dispersed in to pH value, and in detecting solution, adds gradually and contain cupric ion and mercury ion solution to be measured carries out fluorometric titration, waits for and carries out fluorescence spectrum test after 10 minutes.
The present invention is incorporated into two kinds of small molecules heavy metal ion fluorescent probes in hydridization assembling carrier, utilize syntheti c route design cleverly, make the distribution of different fluorescent probe molecules on carrier precisely controlled and realized effective space obstacle, can realize the collaborative detection of two metal ion species simultaneously.
This system can design preparation test material according to detection demand by detecting the fluorescent probe independent assortment of different heavy metal ion, for common two metal ion species that detect, and as the common detection of copper, mercury ion, the common detection of lead, mercury ion etc.Only corresponding probe molecule need to be modified respectively to upper alkynyl, 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 carrying out the detection of different metal ion in water or in organic solvent, and selectivity is good, highly sensitive, strong interference immunity, and efficient.
Test material of the present invention can settle out under the effect of centrifugal force from detect liquid, can realize that heavy metal ion enrichment is with separated, simple and easy to do comparatively easily.
Test material of the present invention can be modified the upper use of multiple matrix (test paper, chip, film etc.) by the sol-gel process in preparation process, has important potential using value.
Accompanying drawing explanation
Fig. 1, Fig. 2 be the mercury ion fluorescence probe with alkynyl group used in embodiment, with 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 outside surface otherness modification characterizes;
Fig. 7 is the infrared spectra in porous silica duct inwall and 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 molecules front and back;
Figure 10 is that two metal ion species fluorescent probe molecules are adding by the uv absorption spectra before and after measured ion;
Figure 11, Figure 12 are test material fluoroscopic examination spectrograms to mercury, two kinds of ions of copper in PBS damping fluid;
Figure 13, Figure 14 are the selectivity sign figure that test material detects cupric ion, mercury ion in PBS damping fluid;
Figure 15 is a routine spherical MCM-41 type porous silica schematic diagram (not removed surfactant templates);
Figure 16 is the schematic diagram that an example is modified with the porous silica of amino group and azido group;
Figure 17 is the schematic 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, cupric ion parallel detection material based on porous silica.
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 large, and the site of controlled chemically modified is many, good stability, and form, large I regulate with the need, and its outside surface and duct inwall all can carry out functional chemically modified.Metal-ion fluorescent probe molecule adopts with the mercury ion fluorescence probe molecule of alkynyl group and carboxy-modified copper ion fluorescence probe molecule, respectively shown in formula I as mentioned in the above, formula II.
Preparation process is as follows:
(1). the preparation of MCM-41 type porous silica
First 1.0 g ionogenic surfactant Trimethyllaurylammonium bromides (CTAB) are dissolved in 480 mL ultrapure waters, add the aqueous solution (NaOH, 2M) of 3.5 mL sodium hydroxide, and the aqueous solution is preheated to 80 ℃.Under mechanical stirring, by dropping funnel, in reaction system, drip 0.5 mL chloropropyl triethoxysilane lentamente, and then dropping 5.0 mL tetraethoxysilane (TEOS, ~ 15 min), reaction mixture is continued at 80 ℃ to reaction 2 hours, and question response is cooled to room temperature after finishing.Filter, collect the precipitation of separating out in process of cooling, successively use ultrapure water and methyl alcohol repetitive scrubbing.Gained filter cake is put into vacuum drying oven dried overnight, and obtaining white powder product is MCM-41 type porous silica; Figure 15 is example spherical this porous silica schematic diagram (not removed surfactant templates).
(2). the preparation of the amido modified porous silica of outside surface
Porous silica 2 g that step (1) is made are scattered in 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 reflux, and reaction is spent the night.After reaction finishes, by the reaction mixture centrifugation purifying of gained, and repeatedly use methanol wash, by products therefrom vacuum-drying.
(3). the removal of surfactant templates
By amido modified porous silica 1.5 g of the outside surface of step (2) gained, be distributed in the hydrochloric methanol solution being 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 to ultrapure water and methyl alcohol repetitive scrubbing, and in vacuum drying oven dried overnight.
(4). the nitrine of porous silica internal surface is functionalized
By the removal of step (2) gained the amido modified porous silica 1g of outside surface of surfactant templates, be scattered in the DMF (DMF) of 100 mL, then in reaction system, add 1g sodiumazide; Gained mixing solutions is heated to 100 ℃, and at this temperature, reacts 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, must be modified with the porous silica (intermediate product M2) above of amino group and azido group; With reference to Figure 16 mono-this porous silica schematic diagram of example.
(5). utilize the azido group of porous silica duct inwall modification of step (4) gained, the amino group of outside surface modification is realized the locator qualification of different heavy metal fluorescent probe molecules;
In 100 mL tri-neck round-bottomed flasks, the intermediate product M2 of 0.7 g step (4) gained is scattered in 50 mL DMF, and adds 400 mg with the mercury ion fluorescence probe of alkynyl; Gained reaction mixture is removed to oxygen 1 hour under normal temperature High Purity Nitrogen air-flow condition, and under nitrogen protection, add successively part 2,2 '-dipyridyl (312 mg, 2.0 mmol) and catalyzer cuprous bromide (143 mg, 1.0 mmol); Reaction mixture is warming up to 60 ℃, and under nitrogen protection condition, reacts 8 hours; Question response mixture is cooled to room temperature, uses successively methyl alcohol, ethylenediamine tetraacetic acid (EDTA) (EDTA) aqueous solution (10 mM), distilled water wash for several times, and centrifugation;
This intermediate product M2 has been modified after mercury ion fluorescence probe molecule, modified subsequently cupric ion is had to the fluorescent probe that selectivity detects.In 100 mL single necked round bottom flask, copper ion fluorescence probe molecule 300 mg with carboxyl are dissolved in to 30 mL tetrahydrofuran (THF)s (THF), and add condensing agent N, N '-dicyclohexylcarbodiimide (0.206 g, 1 mmol), DMAP (12 mg, 0.1mmol) activates half an hour; Then, intermediate product M2 0.5 g that has modified mercury ion fluorescence probe is distributed in reaction mixture to normal-temperature reaction 24 hours.After reaction finishes, reaction mixture is centrifugal, and with methyl alcohol repetitive scrubbing for several times; By the product of gained dried overnight in vacuum drying oven, obtain above-mentioned mercury, cupric ion parallel detection material, electron photomicrograph is shown in Fig. 5, Figure 17 is the schematic diagram of a routine mercury, cupric ion parallel detection material, and the surfaces externally and internally of porous silica is modified with respectively mercury ion fluorescence probe molecule (probe 1), copper ion fluorescence probe molecule (probe 2).
A kind of mercury, cupric ion parallel detection material based on porous silica prepared by aforesaid method
,the ordered porous silicon oxide of MCM-41 type of monodisperse sphere shape of take is carrier, duct inwall, the outside surface of described porous silica are modified with respectively azido group and amino group, mercury ion fluorescence probe molecule and described azido group with 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 20 mL PBS damping fluids (pH 7.0), and in detecting solution, add containing mercury ion or cupric ion solution to be measured and carry out fluorometric titration gradually, wait for and carry out fluorescence spectrum test after 10 minutes.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 shown in Fig. 1,2, Fig. 1 is the nuclear magnetic spectrum of alkynyl-modified mercury ion fluorescence probe used in embodiment, and Fig. 2 is the nuclear magnetic spectrum of the copper ion fluorescence probe of carboxyl modified in 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 after the local amplification of Fig. 4 presentation graphs 3.Fig. 5 represents to modify the porous nano silicon oxide form of organic fluorescent probe, at the skin of inorganic porous silicon oxide, can clearly see the organism thin layer that contrast is slightly low, proves that on porous silica, fluorescent probe molecule is modified successfully.
Fig. 6 is thermal weight loss (TGA) collection of illustrative plates in porous silica duct inwall and 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 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 porous silica inside and outside wall has been modified two kinds of fluorescence molecules front and back.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; Meanwhile, in 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 also proved that 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 measured ion Figure 10, wherein a), b) be the copper ion fluorescence probe with carboxyl, c), d) be the mercury ion fluorescence probe with alkynyl.According to diagram result, mercury ion probe excitation wavelength is chosen as 390nm, and this wavelength can not excite copper ion probe to produce fluorescence; Same, copper ion probe excitation wavelength is chosen as 510nm, and this wavelength can not excite mercury ion probe to produce fluorescence, and two testing processes can not interfere with each other.
Figure 11, Figure 12 represent test material (pH7.0 in 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 fluorescent probe molecule fluorescent emission intensity is changed to 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 test material (pH7.0,0.05g/L) in PBS damping fluid detects mercury ion (λ ex=390 nm), and the selectivity of cupric ion (λ ex=510 nm) characterizes figure, removes Hg in selectivity test
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, can find out that two kinds of fluorescent probe molecules have obvious selectivity to mercury ion, cupric ion respectively.
By specific embodiment, the present invention has been done to detailed explanation above, 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 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 the claims in the present invention.
Claims (10)
1. two metal ion species parallel detection materials based on porous silica, it is characterized in that, this material be take porous silica as carrier, duct inwall, the outside surface of described porous silica are modified with respectively azido group and amino group, the first metal-ion fluorescent probe molecule and described azido group are covalently bound, and the second metal-ion 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, described the first metal-ion fluorescent probe molecule has alkynyl group, and described the second metal-ion fluorescent probe molecule has carboxylic group.
4. material as claimed in claim 1 or 2, it is characterized in that, described the first metal-ion fluorescent probe molecule is the mercury ion fluorescence probe molecule with alkynyl group, and described the second metal-ion 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 fluorescence probe molecule, described copper ion fluorescence probe molecule is respectively suc as formula shown in I, formula II,
。
6. a preparation method for the mercury based on porous silica, cupric ion parallel detection material, is characterized in that, comprises the following steps:
(1). containing in the alkaline aqueous solution of ionogenic surfactant, successively slowly drip volume ratio and be 1 than the chloropropyl triethoxysilane of 8-12 and tetraethoxysilane, and 80 ℃ of reactions, filter, collect gained precipitation, washing, vacuum-drying, obtains MCM-41 type porous silica;
(2). the porous silica that step (1) is obtained is dispersed in to be dissolved with the toluene solution of the aminopropyl-triethoxy siloxanes coupling agent of this porous silica equivalent and reacts, and by reaction mixture centrifugation, obtains intermediate product M1; This intermediate product M1 is the porous silica that outside surface is modified with amino group;
(3). remove step (2) and obtain the surfactant templates in intermediate product M1, make the cl radical of its duct inwall exposed;
(4). with N, dinethylformamide (DMF) is solvent, with the intermediate product M1 of sodiumazide and removal surfactant templates, carry out azido reaction, change the cl radical of the duct inwall of described intermediate product M1 into azido group, obtain 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, first at cuprous bromide, 2, under 2 '-dipyridyl existence condition, utilize click chemistry reaction to make described azido group and mercury ion fluorescence probe molecule covalence graft with alkynyl group; Then, utilize acidylate condensation reaction to make described amino group and carboxy-modified copper ion fluorescence probe molecule covalence graft, obtain described test material.
7. method as claimed in claim 6, is characterized in that, ionogenic surfactant described in step (1) is cetyl trimethylammonium bromide (CTAB).
8. the method as described in claim 6 or 7, is characterized in that,
In step (2), described reaction is to carry out under nitrogen protection condition;
In step (3), the surfactant templates of removing in described intermediate product M1 is to realize in the methanol solution of hydrochloric acid;
In 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 step (5), the structure of the described mercury ion fluorescence probe molecule with alkynyl group, described carboxy-modified copper ion fluorescence probe molecule is respectively suc as formula shown in I, formula II,
。
10. the application of two metal ion species of the test material described in any one claim of claim 1-5 in Parallel Determination water or organic solvent environment.
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| Johann Kecht 等.Selective Functionalization of the Outer and Inner Surfaces in Mesoporous Silica Nanoparticles.《Chem. Mater.》.2008,第20卷(第23期), |
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