CN113861964B - Inorganic hybridization probe and preparation method and application thereof - Google Patents

Inorganic hybridization probe and preparation method and application thereof Download PDF

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CN113861964B
CN113861964B CN202111211527.5A CN202111211527A CN113861964B CN 113861964 B CN113861964 B CN 113861964B CN 202111211527 A CN202111211527 A CN 202111211527A CN 113861964 B CN113861964 B CN 113861964B
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rare earth
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montmorillonite
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europium
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CN113861964A (en
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王前明
郭志成
郑玉惠
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South China Normal University
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Abstract

The invention provides an inorganic hybridization probe, a preparation method and application thereof. The method solves the problem of insufficient thermal stability of the rare earth organic complex, provides a convenient and feasible method for detecting copper ions and dichromate ions, and has corresponding fluorescence spectrum detection limits of 13nM and 38nM respectively.

Description

Inorganic hybridization probe and preparation method and application thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an inorganic hybridization probe, a preparation method and application thereof.
Background
Copper ion as one of essential trace elements plays an important role in metabolism of human body, such as Cu 2+ Takes part in the enzyme catalysis process, is also a component part of copper proteins such as human blood, liver, brain tissue and the like, and is Cu in human body 2+ Too low a content may cause diseases such as osteoporosis and anemia, while too high a content may cause diseases such as elevated blood pressure, alzheimer's disease and Wilson's disease. But at the same time Cu 2+ Also a common environmentally contaminated transition metal ion, excessive copper ions in soil may be detrimental to the growth of crops and may greatly damage the liver and kidneys of organisms by accumulation of contaminated food and drinking water in the organisms. Cr (Cr) 2 O 7 2- As a strong oxidizing agent, which is common in laboratories, also has adverse effects on human health, such as causing skin diseases and lung cancer, stimulating respiratory systems, damaging liver and kidneys, etc., the anions also diffuse into the environment through processes such as metal plating, paint pigment production, and leather production. Thus, for Cu 2+ And Cr (V) 2 O 7 2- Is of great importance for environmental protection and human health.
The existing methods for detecting anions and cations comprise an atomic absorption spectrometry, an atomic fluorescence spectrometry, an inductively coupled plasma mass spectrometry, a surface enhanced Raman spectrometry, a biosensing method, an electrochemical method and the like, but the methods have the defects of complex process, high cost, inapplicability to field analysis, inapplicability to mass detection and the like. The fluorescence detection is widely applied to detection of various anions and cations and organic compounds due to good selectivity, high sensitivity and rapid response, but most fluorescence probes cannot eliminate interference of background signals, so that accuracy of detection results is affected.
The rare earth organic complex fluorescent probe receives a lot of attention because of its special spectral characteristics such as sharp emission peak, long fluorescence lifetime, large stokes shift, etc., which helps to eliminate the influence of background signal. However, because the f-f transition of the rare earth ion is forbidden transition, larger energy is needed for directly exciting the rare earth ion, and the rare earth ion luminescence can be sensitized through an antenna effect by utilizing some organic ligands including beta-diketone, aromatic carboxylic acid, bipyridine, phenanthroline, triphenylphosphine oxide, macrocyclic crown ether and the like, so that the rare earth organic complex fluorescent probe is constructed. However, rare earth organic complexes still have the defect of insufficient light and heat stability, which limits the application of the rare earth organic complexes.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the first aspect of the invention provides an inorganic hybridization probe which not only solves the problem of insufficient thermal stability of rare earth organic complexes, but also provides a feasible method for detecting copper ions and dichromate ions.
The second aspect of the invention provides a preparation method of the inorganic hybridization probe.
The third aspect of the invention provides an application of the inorganic hybridization probe.
According to a first aspect of the present invention, there is provided an inorganic hybrid probe comprising an inorganic matrix and a rare earth organic complex, the inorganic matrix and the rare earth organic complex being covalently bound, the inorganic matrix comprising a silanized layered mineral.
According to the invention, the silanized layered mineral can be covalently bonded with the rare earth organic complex to form the inorganic-organic hybridization fluorescent probe with good thermal stability, wherein the layered mineral is used as an inorganic matrix to be bonded with the rare earth organic complex, so that the problem of insufficient thermal stability of the rare earth organic complex is solved, the silanized layered mineral has a larger specific surface area, and the detection limit of fluorescence response to objects is reduced after the silanized layered mineral is covalently bonded with the rare earth organic complex, so that the detection sensitivity of the inorganic hybridization probe to metal salt ions is improved.
In some embodiments of the invention, the molar ratio of the inorganic matrix to the rare earth organic complex is 1:1.
in some preferred embodiments of the present invention, the silanized layered mineral is a layered mineral modified with a silane coupling agent, which is at least one selected from the group consisting of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane. In the invention, the silane coupling agent is-Si-OCH 2 CH 3 Can be covalently bonded to-OH groups in layered minerals and carry-NH 2 The functional group silane coupling agent can be combined with the lamellar mineral to obtain the aminated modified lamellar mineral, which can react with the rare earth organic complex to form covalent bonding.
In some more preferred embodiments of the invention, the layered mineral is selected from at least one of montmorillonite, kaolin, hydrotalcite-like compounds. Wherein the montmorillonite has the chemical formula of [ (Na, ca) 0.33 (Al,Mg) 2 (Si 4 O 10 )(OH) 2 ·nH 2 O]The montmorillonite as one kind of TOT type inorganic clay mineral has structure features that one layer of alumina octahedron is sandwiched between two layers of silica tetrahedron, and has unique layered structure and may be chemically modified with silane coupling agent via the hydroxyl functional group contained in the montmorillonite. The main mineral component of the kaolin is kaolinite, and the chemical formula of the crystal is 2SiO 2 ·Al 2 O 3 ·2H 2 O, kaolin minerals belong to 1:1 layered silicate, and the crystal mainly comprises silicon oxygen tetrahedrons and aluminum oxyhydrogen octahedrons, wherein the silicon oxygen tetrahedrons are connected in a two-dimensional direction in a common vertex angle mode to form a grid layer in a hexagonal arrangement, and the tip oxygen which is not commonly used by each silicon oxygen tetrahedron faces one side; the unit layer is composed of a 1:1 unit layer composed of a silicon oxygen tetrahedron layer and a pointed oxygen of the oxygen-bearing octahedral layer. The hydroxyl functional groups of the kaolin itself can be chemically modified with the silane coupling agent; hydrotalcite and hydrotalcite-like compounds are collectively referred to as layered double hydroxides, typical hydrotalcite-like compounds being magnesium aluminum carbonate hydrotalcite: mg of 6 Al 2 (OH) 16 CO 3 ·4H 2 O, the laminate of which consists of magnesium octahedra and aluminum oxide octahedra. The hydroxyl functional groups in hydrotalcite and hydrotalcite-like compounds can be chemically modified with silane coupling agents. The layered minerals can be covalently bonded with the silane coupling agent, and the thermal stability of the rare earth complex can be improved by virtue of the good thermal stability of the inorganic matrix.
In some more preferred embodiments of the present invention, the preparation raw materials of the rare earth organic complex include rare earth ions, a first ligand selected from any one of Diethyl Triamine Pentaacetic Acid (DTPA) and ethylenediamine tetraacetic acid (EDTA), and a second ligand including any one of 2-Thenoyl Trifluoroacetone (TTA), trifluoroacetylacetone, 4-trifluoro-1-phenyl-1, 3-butanedione, 4-trifluoro-1- (2-naphthyl) -1, 3-butanedione. In the invention, the rare earth organic complex is preferably an organic complex containing carboxyl, can react with the silanized lamellar mineral to form an amide bond for bonding, and DTPA and EDTA are used as a polydentate ligand, contain more amino nitrogen atoms and carboxyl oxygen atoms which can be used for coordinating with rare earth ions, so that the rare earth organic complex can be bonded with the rare earth ions very firmly, and can be covalently bonded with the silanized lamellar mineral through carboxyl in the first ligand. The second ligand should be a beta-diketone compound which functions to chelate and coordinate with the rare earth ion through the oxygen atom in the beta-diketone thereof and to sensitize the rare earth ion to emit light through the antenna effect.
In some more preferred embodiments of the present invention, the rare earth ion is selected from Eu 3+ 、Tb 3+ Any one of the following.
According to a second aspect of the present invention, there is provided a method for preparing the above inorganic hybrid probe, comprising the steps of:
s1: the lamellar mineral and the silane coupling agent undergo an amination reaction to prepare a silanized lamellar mineral;
s2: and (3) after the first ligand solution and the silanized layered mineral are subjected to carboxylation reaction under the action of an activating agent, mixing and reacting with a soluble salt containing rare earth ions and a second ligand in sequence to prepare the inorganic hybridization probe.
In some embodiments of the invention, in S2, the activator is selected from the group consisting of a combination of N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, or is N, N-diisopropylethylamine. The activator is capable of activating the carboxyl functionality of the first ligand to promote the reaction of the carboxyl group with the amino functionality of the silanized layered mineral to produce an amide bond, thereby forming a covalent bond.
In some preferred embodiments of the present invention, the soluble salt containing rare earth ions is selected from Eu (NO 3 ) 3 ·6H 2 O、Tb(NO 3 ) 3 ·6H 2 O.
In some more preferred embodiments of the present invention, the reaction temperature of the amination reaction in S1 is 50℃to 60℃and the reaction time is 24h to 48h.
In some more preferred embodiments of the present invention, the solvent for the amination reaction in S1 is absolute ethanol.
In some more preferred embodiments of the present invention, the carboxylation reaction in S2 is carried out at a reaction temperature of 60 ℃ to 75 ℃ for a reaction time of 1h to 3h.
In some more preferred embodiments of the present invention, the solvent for the carboxylation reaction in S2 is dimethyl sulfoxide.
In some more preferred embodiments of the present invention, the reaction temperature of the mixing reaction in S2 is 18-35 ℃ and the reaction time is 4-8 hours.
In some more preferred embodiments of the present invention, the solvent for the mixing reaction in S2 is absolute ethanol.
In some more preferred embodiments of the present invention, the method for preparing an inorganic hybridization probe further comprises a step of purifying each reaction product; preferably, the purification comprises separation, washing and drying; further preferably, the washing is performed using each reaction solvent and deionized water.
According to a third aspect of the present invention, there is provided the use of an inorganic hybridization probe as described above for detecting metal salt ions.
In some embodiments of the invention, the metal salt ion comprises Cu 2+ 、Fe 3+ 、Ag + 、Ni 2+ 、Co 2+ 、Cd 2+ 、Al 3+ 、Cr 3+ 、Zn 2+ 、Mg 2+ 、Cr 2 O 7 2- 、MnO 4 - 、NO 2 - 、F - 、Cl - 、Br - 、S 2- 、S 2 O 3 2- 、SCN - 、PO 4 3- At least one of them.
In some preferred embodiments of the present invention, the metal salt ion comprises Cu 2+ 、Cr 2 O 7 2- At least one of them.
The beneficial effects of the invention are as follows:
1. in the invention, the lamellar mineral is used as an inorganic matrix to be combined with the rare earth organic complex, so that the thermal stability of the hybrid material is obviously improved compared with that of a single rare earth complex, and the problem of insufficient thermal stability of the rare earth complex is solved.
2. In the invention, the lamellar mineral is of a lamellar structure, has larger specific surface area, and is favorable for reducing the detection limit of fluorescence response to the object after being covalently combined with the rare earth organic complex.
3. In the rare earth organic complex, the first ligand is a multidentate ligand, can be firmly combined with rare earth ions through containing a plurality of nitrogen atoms and oxygen atoms in molecules, and the second ligand 2-Thenoyl Trifluoroacetone (TTA) can effectively sensitize the rare earth ions to emit light through a beta-diketone structure, so that the energy required for exciting the rare earth ions to emit light is reduced.
4. The hybrid inorganic probe can realize Cu 2+ With Cr 2 O 7 2- Having ions thereinAnd (3) effective detection, wherein the detection limit of the corresponding fluorescence spectrum is 13nM and 38nM respectively.
5. The hybrid inorganic probe of the invention can be used for Cu 2+ With Cr 2 O 7 2- Ion-implemented differential detection, cr 2 O 7 2- The ions can be detected by fluorescence spectrum, or by observing Cr in the solution 2 O 7 2- Detecting the variation trend of the absorption peak of the hybrid material in the ultraviolet-visible light region when the ion concentration is increased, and obtaining Cr by an ultraviolet-visible light spectrophotometer 2 O 7 2- The detection limit of the ions was 108nM and, with Cr 2 O 7 2- The ion concentration is increased, the appearance of the hybrid material solution is also changed, the light white color is gradually changed into yellow brown, and direct visual observation can be realized.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a synthetic route diagram of montmorillonite-europium (III) organic complex of example 1 of the present invention;
FIG. 2 is an SEM image of an organic montmorillonite-europium (III) complex of example 1 of the present invention, where a has a scale of 0.2 μm and b has a scale of 100nm;
FIG. 3 is a TEM image of the organic montmorillonite-europium (III) complex of example 1 of the present invention, in which a has a scale of 0.2um and b has a scale of 100nm;
FIG. 4 is an infrared spectrum of the organic montmorillonite-europium (III) complex of example 1 of the present invention;
FIG. 5 is an ultraviolet-visible spectrophotometric diagram of the montmorillonite-europium (III) organic complex of example 1 of the present invention;
FIG. 6 is an X-ray photoelectron spectrum of a montmorillonite-europium (III) organic complex of example 1 of the present invention;
FIG. 7 is a fluorescence spectrum of montmorillonite-europium (III) organic complex of example 1 of the present invention;
FIG. 8 shows the results of thermogravimetric analysis of the montmorillonite-europium (III) organic complex of example 1 and the europium (III) organic complex of comparative example of the present invention;
FIG. 9 shows the fluorescence quenching effect of the montmorillonite-europium (III) organic complex of example 1 on different cations (a) and anions (b);
FIG. 10 shows the results of the montmorillonite-europium (III) organic complex of example 1 of the present invention for CuCl of various concentrations 2 A fluorescence intensity change graph (a) of the solution and a corresponding linear regression equation (b) for different concentrations K 2 Cr 2 O 7 A fluorescence intensity change graph (c) of the solution and a corresponding linear regression equation (d);
FIG. 11 is a plot of the response behavior of montmorillonite-europium (III) organic complexes of example 1 to various metal salt ions;
FIG. 12 shows the Cr concentration 2 O 7 2- Example 1 below the trend of the ultraviolet-visible light absorption (a) of the montmorillonite-europium (III) organic complex and the corresponding linear regression equation (b).
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
FIG. 1 is a synthetic route diagram of montmorillonite-europium (III) organic complex in the present invention, and as shown in FIG. 1, an inorganic hybrid probe is prepared in this example, and the specific process is as follows:
s1: montmorillonite amination reaction: ratio 1 of the amounts of the substances: (1-2) montmorillonite (MMT) and 3-aminopropyl triethoxysilane were weighed into a 100mL round bottom flask, and 30mL of absolute ethanol was added, and ultrasound was applied for 3min to fully disperse montmorillonite in absolute ethanol. The montmorillonite suspension was transferred to a sand bath at 50℃and magnetically stirred at 600rpm for 24h. Centrifuging the mixture at 6000rpm for 5min after the reaction, washing with anhydrous ethanol and deionized water three times, and vacuum drying at 70deg.CDrying in a box for 10 hours, the white powder obtained was designated MMT-NH 2 ；
S2: carboxylation reaction: the ratio of the amounts of the substances is (1-2): 1 weighing diethylenetriamine pentaacetic acid (DTPA) and MMT-NH obtained by S1 2 And added to two beakers with 10mL of deionized water, respectively, sonicated for 5min, heated in a 60 ℃ sand bath and magnetically stirred at 750rpm until DTPA was completely dissolved. N-hydroxysuccinimide (NHS) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) were weighed in an amount 3 to 5 times the amount of the DTPA substance in 20mL of dimethyl sulfoxide, and were sufficiently dissolved by sonication for 3 minutes, and the DMSO solution was slowly dropped into an aqueous solution of DTPA at a rate of 1 drop/second, and the mixed solution was subjected to a carboxyl activation reaction at 60℃for 1 hour. MMT-NH is then applied 2 Slowly drop into the mixed solution, and react for 12 hours at 60 ℃ with heating and stirring. The resulting mixture was centrifuged at 6000rpm for 5min, washed sequentially with dimethyl sulfoxide and deionized water for 3 times, and dried in a vacuum oven at 70℃for 12h. The resulting white solid was designated MMT-DTPA;
s3: the ratio of the amounts of the substances is 1:1 weighing Eu (NO) 3 ) 3 ·6H 2 The MMT-DTPA obtained by O and S2 is slowly dropped into a 50mL round bottom flask containing 20mL absolute ethyl alcohol, and ammonia water solution with mass fraction of 25% or NaOH solution with concentration of 0.1mol/L is slowly dropped until the pH value of the solution is 8-9, after fully dispersing in ultrasound for 3min, the mixture is stirred at room temperature for 5h at 600 rpm. Centrifuging the mixture at 6000rpm for 5min, washing with absolute ethanol and deionized water for 3 times, and drying in a vacuum drying oven at 70deg.C for 12 hr to obtain white solid called MMT-DTPA-Eu;
s4: the ratio of the amounts of the substances (1 to 2): 1 weighing 2-Thenoyl Trifluoroacetone (TTA) and solid MMT-DTPA-Eu obtained by S3 into a 50mL round bottom flask containing 20mL absolute ethyl alcohol, slowly dropwise adding ammonia water with the mass fraction of 25% or NaOH solution with the concentration of 0.1mol/L to adjust the pH value of the solution to 8-9, and reacting the mixture at room temperature for 5 hours at the magnetic stirring speed of 600 rpm. The mixture was centrifuged at 6000rpm for 5min, washed sequentially with absolute ethanol and deionized water for 3 times, dried in a vacuum oven at 70℃for 12h, and the resulting white solid was designated MMT-DTPA-Eu-TTA.
Comparative example
The comparative example prepared an europium (III) organic complex, which differs from example 1 in that the europium (III) organic complex is not covalently bound to montmorillonite by the following procedure:
the ratio of the amounts of the substances is 1:1, weighing Diethyl Triamine Pentaacetic Acid (DTPA) and europium nitrate hexahydrate, adding the mixture into a round-bottom flask, adding 20mL of deionized water, and slowly dropwise adding an ammonia water solution with the mass fraction of 25% or a NaOH solution with the mass fraction of 0.1mol/L until the pH value of the solution is 8-9; eu (NO) 3 ) 3 ·6H 2 0.1-2 times of the mass, 2-Thiophenecarboxyl Trifluoroacetone (TTA) is weighed and dissolved in 20mL of absolute ethyl alcohol, the TTA solution is slowly added into an aqueous solution of DTPA and europium nitrate, the mixture is magnetically stirred for 5h at the room temperature and the rotation speed of 600rpm, the mixture is centrifuged for 5min at the rotation speed of 6000rpm, the mixture is washed for 3 times by absolute ethyl alcohol and deionized water in sequence, and the mixture is dried in a vacuum drying oven at 70 ℃ for 12h, so that white solid which is marked as DTPA-Eu-TTA is obtained.
Test examples
The montmorillonite-europium (III) organic complex (MMT-DTPA-Eu-TTA) prepared in example 1 was characterized and tested for fluorescence response by using a field emission scanning electron microscope SEM, a field emission transmission electron microscope TEM, a Fourier transform infrared spectrometer, an ultraviolet-visible spectrophotometer, an X-ray electron spectrometer, a fluorescence spectrometer, a thermogravimetric analyzer and other instruments, and the specific operations are:
field emission scanning electron microscope SEM test: dispersing a trace amount of montmorillonite-europium (III) organic complex in absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, dripping 1-2 drops of the organic complex on a clean monocrystalline silicon wafer by using a dropper, placing the monocrystalline silicon wafer in a vacuum drying oven at 70 ℃, drying the monocrystalline silicon wafer for 6h, fixing the monocrystalline silicon wafer on a carrier by using conductive adhesive, and observing the morphology of the montmorillonite-europium (III) organic complex through a field emission Scanning Electron Microscope (SEM) after gold plating treatment.
The scanning electron microscope test result is shown in FIG. 2, wherein a is a montmorillonite-europium (III) complex SEM image with a scale of 0.2 μm, and b is a montmorillonite-europium (III) complex SEM image with a scale of 100nm. It can be observed that the montmorillonite-europium (III) complex is an irregular lamellar structure, and the transverse dimension of the single lamellar structure is in the micron level, and the montmorillonite-europium (III) complex has a relatively large specific surface area.
Field emission transmission electron microscope TEM testing: dispersing a trace amount of montmorillonite-europium (III) organic complex in absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, dripping 1 drop by using a dropper on a clean copper mesh, and observing the morphology of the montmorillonite-europium (III) organic complex by using a field emission Transmission Electron Microscope (TEM).
The transmission electron microscope test results are shown in FIG. 3, wherein the scale of a is 0.2um, and the scale of b is 100nm. It can be seen that the morphology of the montmorillonite-europium (III) organic complex is characterized in that the montmorillonite-europium (III) organic complex is formed by continuously stacking a plurality of sheets and has an irregular layered structure, the test result is matched with a scanning electron microscope, and the relatively large specific surface area of the montmorillonite is beneficial to providing more reaction sites and reducing the detection limit of fluorescence response to objects.
Fourier transform infrared spectrum testing: 200mg of potassium bromide is weighed and placed in a vacuum drying oven at 60 ℃, 150mg of potassium bromide and a trace amount of montmorillonite-europium (III) organic complex are mixed in a clean mortar after drying for 6 hours, tabletting is carried out after grinding for 10 minutes, and the functional groups contained in the montmorillonite-europium (III) organic complex are analyzed by a Fourier transform infrared spectrometer.
The IR spectrum is shown in FIG. 4, which shows 3619cm -1 Is the stretching vibration of O-H group in carboxyl derived from Diethyl Triamine Pentaacetic Acid (DTPA), 3418cm -1 Is subjected to stretching vibration of 3059cm of N-H groups derived from a silane coupling agent and DTPA -1 Is thiophene ring sp from 2-thiophene formyl trifluoroacetone (TTA) 2 Stretching vibration of hybridized C-H group, 2930cm -1 Is derived from silane coupling agent and DTPA-CH 2 -stretching vibration of the radical, 1591cm -1 Is characterized in that C=O group in beta-diketone structure of DTPA and TTA is subjected to stretching vibration of 1410cm -1 Is vibrated by C-F groups derived from TTA, 1214cm -1 Is the stretching vibration of Si-C group from silane coupling agent and 1034cm -1 The Si-O group is subjected to stretching vibration to obtain 3The aminopropyl triethoxy silane is successfully combined with montmorillonite by covalent bond, amide bond is formed, and two organic ligands DTPA and TTA are successfully combined with Eu 3+ Coordination is performed.
Ultraviolet-visible spectrophotometer test: dispersing montmorillonite-europium (III) organic complex in deionized water with the concentration of 0.1mg/mL, adding deionized water into two clean quartz cuvettes, taking out the cuvette outside after testing a baseline by using an ultraviolet-visible spectrophotometer, replacing the cuvette with a suspension of the montmorillonite-europium (III) organic complex, and testing the distribution of absorption peaks of the montmorillonite-europium (III) organic complex in the wavelength range of 200 nm-800 nm.
The ultraviolet-visible spectrophotometer test is shown in fig. 5, and the result is that the absorption at 342nm is from pi-pi electron transition of carbon-carbon double bond in the second ligand 2-Thenoyl Trifluoroacetone (TTA), which proves that TTA participates in the structure composition of the hybrid material, and the result is consistent with the result of infrared spectrum test.
X-ray photoelectron spectroscopy (XPS) test: 50mg of montmorillonite-europium (III) organic complex is weighed, added into a mortar for grinding for 20min, fully ground, placed in a vacuum drying oven at 60 ℃ for 6h for preservation, 10 mg-20 mg of sample is taken, and the type of the contained elements is qualitatively analyzed by an XPS instrument.
XPS analysis is shown in FIG. 6, wherein 103.51eV, 286.51eV, 401.91eV, 534.01eV and 1167.01eV respectively correspond to the binding energies of Si 2p, C1 s, N1 s, O1 s and Eu 3d, and europium is contained in the detected element types, which proves that the europium (III) organic complex is successfully bound with montmorillonite through covalent bonds.
Fluorescence spectrometer test: dispersing montmorillonite-europium (III) organic complex in deionized water with the concentration of 1mg/mL, taking 2mL of the dispersion liquid in a four-way quartz cuvette, and testing the fluorescence emission condition by using a fluorescence spectrometer.
The test result of the fluorescence spectrometer is shown in FIG. 7, wherein a is an excitation spectrum, and the maximum excitation wavelength is 373nm; b is an emission spectrum, and can observe emission peaks of 582nm, 596nm, 615nm and 656nm, which respectively correspond to characteristic emission peaks of europium 5 D 0 → 7 F 0 、 5 D 0 → 7 F 1 、 5 D 0 → 7 F 2 And 5 D 0 → 7 F 3 a transition); the strongest emission peak at 615nm was that of europium ions 5 D 0 → 7 F 2 The energy level transition is caused, so that the montmorillonite-europium complex can observe red fluorescence under 365nm light excitation.
The thermal stability of the montmorillonite-europium (III) organic complex is analyzed by using a thermogravimetric analyzer, and the specific operation is as follows:
(1) Control group: two clean small crucibles are put into a hearth of a thermogravimetric analyzer, the small crucible at the outer side is taken out after clearing, 5mg of europium (III) organic complex (DTPA-Eu-TTA) prepared in comparative example is added, and the change process of the mass of the sample along with the temperature rise in the range of 25-800 ℃ is observed.
(2) Experimental group: two clean small crucibles are put into a hearth of a thermogravimetric analyzer, the small crucibles at the outer side are taken out after clearing, 5mg of montmorillonite-europium (III) organic complex (MMT-DTPA-Eu-TTA) prepared in example 1 is added, and the change process of the mass of the sample along with the temperature rise in the range of 25-800 ℃ is observed.
As shown in FIG. 8, the mass reduction of DTPA-Eu-TTA and MMT-DTPA-Eu-TTA is similar in the heating process at 25-150 ℃, but the mass reduction of the DTPA-Eu-TTA is more remarkable in the heating process at 150-800 ℃, and the mass reduction of DTPA-Eu-TTA is 60% in the heating process at 800 ℃, and the mass reduction of MMT-DTPA-Eu-TTA is only 25%, so that the thermal stability of MMT-DTPA-Eu-TTA is higher than that of DTPA-Eu-TTA.
Example 2
This example tests the fluorescence response behavior of the montmorillonite-europium (III) organic complex prepared in example 1 to different metal salts, and it specifically comprises the following steps:
(1) Blank group: the montmorillonite-europium (III) organic complex is dispersed in deionized water and the concentration is 1mg/mL, 2mL is taken in a test tube, the suspension is irradiated by light with the wavelength of 395nm, and the luminescence condition is observed.
(2) Experiment group 1: the montmorillonite-europium (III) organic complex was dispersed in deionized water at a concentration of 1mg/mL, 2mL was taken in a test tube, 2. Mu.L of NaCl solution at a concentration of 0.001mol/mL was added to the test tube by a pipette, and the suspension was irradiated with light having a wavelength of 395nm to observe the luminescence.
(3) Experimental group 2-20: the difference from experiment group 1 is that 0.001mol/mL NaCl solution is replaced by CuCl 2 、FeCl 3 、AgNO 3 、NiCl 2 、Co(NO 3 ) 2 、Cd(NO 3 ) 2 、Al 2 (SO 4 ) 3 、CrCl 3 、ZnCl 2 、MgSO 4 、K 2 Cr 2 O 7 、KMnO 4 、NaNO 2 、NaF、NaBr、Na 2 S、Na 2 S 2 O 3 、KSCN、Na 3 PO 4 The suspension was then irradiated with light having a wavelength of 395nm, and the luminescence thereof was observed.
The test results of the fluorescence spectrometer are shown in fig. 9, wherein graphs a and b respectively show the fluorescence quenching effect of montmorillonite-europium (III) organic complexes after different cations and anions are introduced. The single montmorillonite-europium (III) organic complex aqueous suspension exhibits red fluorescence under irradiation of ultraviolet light of 395nm wavelength; in fluorescence response behavior to cations, cu 2+ The fluorescent quenching effect on montmorillonite-europium (III) complex is most obvious, and the response behavior of other cations is poor; cr in fluorescence response behavior to anions 2 O 7 2- The fluorescent quenching effect on the montmorillonite-europium (III) organic complex is most obvious, and the response behavior of other anions is poorer, therefore, the aqueous suspension of the montmorillonite-europium (III) organic complex can be used as a fluorescent detection probe of metal salt ions, wherein the fluorescent detection probe has the effect on Cu 2+ And Cr (V) 2 O 7 2- The fluorescence response quenching effect of the two objects is most obvious.
Example 3
This example demonstrates the measurement of the organic montmorillonite-europium (III) complex prepared in example 1 for various concentrations of CuCl 2 And K 2 Cr 2 O 7 The fluorescence intensity of the solution changes, and the specific process is as follows:
dispersing montmorillonite-europium (III) organic complex in deionized water with the concentration of 1mg/mL, taking 2mL of the dispersion liquid in a four-way quartz cuvette, and preparing CuCl with the concentration of 1-20 mu M 2 And K 2 Cr 2 O 7 Solution, drop 10 μl into aqueous suspension of montmorillonite-europium (III) complex by pipetting gun, and observe fluorescence intensity of montmorillonite-europium (III) organic complex along with CuCl in aqueous solution under 373nm wavelength light irradiation by fluorescence spectrometer 2 Or K 2 Cr 2 O 7 The concentration increases, and the fluorescence intensity tends to change.
The test results of the fluorescence spectrometer are shown in FIG. 10, wherein graphs a and c respectively show the fluorescence intensity of the montmorillonite-europium (III) organic complex with CuCl in aqueous solution 2 Or K 2 Cr 2 O 7 The concentration is continuously increased, the fluorescence intensity is gradually weakened, the pink solution at the upper right part in the figure a is a fluorescence emission diagram of a single montmorillonite-europium (III) organic complex suspension, and the semitransparent solution is dropwise added Cu 2+ Fluorescent emission of the ionic post-montmorillonite-europium (III) organic complex suspension; in the fluorescent emission pattern of the single montmorillonite-europium (III) organic complex suspension as pink solution in the pattern c, the Cr is added dropwise as light pink solution 2 O 7 2- Fluorescent emission of the ionic post-montmorillonite-europium (III) organic complex suspension; the linear regression equations corresponding to the graphs b and d respectively calculate Cu 2+ And Cr (V) 2 O 7 2- The fluorescence detection limits of the ions were 13nM and 38nM, respectively.
Example 4
This example tests the response behavior of the organic montmorillonite-europium (III) complex prepared in example 1 to different metal salt ions, and under the condition of no ultraviolet irradiation, different metal salt solutions were added to the aqueous suspension of the montmorillonite-europium (III) complex, and the change in the appearance of the suspension was observed, specifically by the following steps:
(1) Blank group: montmorillonite-europium (III) complex is dispersed in deionized water and the concentration of the montmorillonite-europium (III) complex is 1mg/mL, 1mL is taken in a glass bottle, and the appearance of the suspension is observed.
(2) Experiment group 1: montmorillonite-europium (III) complex was dispersed in deionized water at a concentration of 1mg/mL, 1mL was taken in a glass bottle, and after 10. Mu.l of NaCl solution at a concentration of 0.001mol/mL was added to the aqueous solution using a pipette, the change in appearance of the suspension was observed.
(3) Experimental group 2-20: the difference from experiment group 1 is that 0.001mol/mL NaCl solution is replaced by CuCl 2 、FeCl 3 、AgNO 3 、NiCl 2 、Co(NO 3 ) 2 、Cd(NO 3 ) 2 、Al 2 (SO 4 ) 3 、CrCl 3 、ZnCl 2 、MgSO 4 、K 2 Cr 2 O 7 、KMnO 4 、NaNO 2 、NaF、NaBr、Na 2 S、Na 2 S 2 O 3 、KSCN、Na 3 PO 4 And the appearance of the suspension after addition of the different metal salt solutions was observed.
The results of the experiment are shown in FIG. 11, wherein the appearance of the aqueous suspension of the single montmorillonite-europium (III) complex is light white; after adding K 2 Cr 2 O 7 After the solution, the color of the suspension is changed from light white to yellow brown, and the appearance of the dispersion is not changed by the rest metal salt, so the montmorillonite-europium (III) complex prepared by the invention can realize Cu 2+ And Cr (V) 2 O 7 2- The response behavior of the two objects is distinguished.
Example 5
In this example, the K in the aqueous solution was observed by means of an ultraviolet-visible spectrophotometer 2 Cr 2 O 7 The concentration increase is used for changing the absorption peak of montmorillonite-europium (III) complex in the range of 200 nm-800 nm, and the specific process is as follows:
dispersing montmorillonite-europium (III) organic complex in deionized water with the concentration of 0.1mg/mL and preparing K with the concentration of 1 mM-10 mM 2 Cr 2 O 7 A solution. Deionized water is added into two clean quartz cuvettes, and an ultraviolet-visible spectrophotometer is used for testing the baseA wire.
Blank group: taking out the external cuvette, replacing the cuvette with a montmorillonite-europium (III) organic complex suspension, and testing the light absorption condition in the wavelength range of 200 nm-800 nm;
experimental group: taking out the outer cuvette, washing the cuvette, adding 2mL of montmorillonite-europium (III) organic complex suspension, and dripping 2 μl of K with concentration of 1 mM-10 mM with a pipetting gun 2 Cr 2 O 7 Solution, observe K 2 Cr 2 O 7 The concentration gradually increases from 1 mu M to 10 mu M, and the distribution of absorption peaks of the montmorillonite-europium (III) complex is changed in the range of 200nm to 800 nm.
The result of the ultraviolet-visible spectrophotometer is shown in FIG. 12, and graphs a and b represent Cr, respectively 2 O 7 2- The ultraviolet-visible light absorption value change trend and the corresponding linear regression equation of the hybrid material when the concentration is increased, wherein the upper right diagram in the figure a is a schematic diagram of the appearance of the water suspension of the single montmorillonite-europium (III) complex; the right image of the illustration shows the dropping of K 2 Cr 2 O 7 The appearance of the aqueous suspension of the montmorillonite-europium (III) complex after the solution is schematically shown. It was observed that the aqueous suspension of the single montmorillonite-europium (III) organic complex had only one absorption peak at 342nm, with Cr in solution 2 O 7 2- The intensity of the absorption peak gradually decreases and a red shift phenomenon occurs, and a new absorption peak appears at about 245nm wavelength, and a single K 2 Cr 2 O 7 The absorption conditions of ultraviolet-visible light of the solution are similar; the detection limit obtained by analysis with an ultraviolet-visible spectrophotometer was 108nM, based on the linear regression equation.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (6)

1. An inorganic hybrid probe, characterized in that: the inorganic matrix comprises a silanized layered mineral and a rare earth organic complex, wherein the inorganic matrix and the rare earth organic complex are covalently bonded;
the preparation raw materials of the rare earth organic complex comprise rare earth ions, a first ligand and a second ligand, wherein the first ligand is selected from any one of diethyl triamine pentaacetic acid and ethylenediamine tetraacetic acid, and the second ligand is selected from any one of 2-thenoyl trifluoroacetone, trifluoroacetylacetone, 4-trifluoro-1-phenyl-1, 3-butanedione and 4, 4-trifluoro-1- (2-naphthyl) -1, 3-butanedione;
the rare earth ion is selected from Eu 3+ 、Tb 3+ Any one of them;
the silanized lamellar mineral is a lamellar mineral modified by a silane coupling agent, and the silane coupling agent is at least one selected from 3-aminopropyl triethoxysilane and 3-aminopropyl trimethoxysilane;
the first ligand is combined with the rare earth ion, and the oxygen atom in the second ligand is chelated and coordinated with the rare earth ion; the carboxyl group of the first ligand in the rare earth organic complex is covalently bound with the silanized layered mineral.
2. The inorganic hybrid probe according to claim 1, wherein: the mol ratio of the inorganic matrix to the rare earth organic complex is 1:1.
3. the inorganic hybrid probe according to claim 1, wherein: the layered mineral is at least one selected from montmorillonite, kaolin, hydrotalcite and hydrotalcite-like compound.
4. A method for preparing the inorganic hybrid probe according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
s1: the lamellar mineral and the silane coupling agent undergo an amination reaction to prepare a silanized lamellar mineral;
s2: and (3) after the first ligand solution and the silanized layered mineral are subjected to carboxylation reaction under the action of an activating agent, mixing and reacting with a soluble salt containing rare earth ions and a second ligand in sequence to prepare the inorganic hybridization probe.
5. The method for preparing an inorganic hybridization probe according to claim 4, wherein: in S2, the activator is selected from the group consisting of N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, or N, N-diisopropylethylamine.
6. Use of an inorganic hybrid probe according to any one of claims 1 to 3 for detecting metal salt ions selected from Cu 2+ 、Cr 2 O 7 2- At least one of them.
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CN101671557A (en) * 2009-10-21 2010-03-17 上海交通大学 Preparation method of clay base fluorescent probe
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