CN108593610A - A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF - Google Patents
A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF Download PDFInfo
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Abstract
The preparation method of the invention discloses a kind of Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV MOF.By the way that suspension is made in the coordination bond material of nano molecular tong-like metal-organic framework material and metal ion, it is evenly coated on chromatographic paper, test paper of the present invention is obtained after dry.Nano molecular tong-like metal-organic framework material used in test paper of the present invention has specific surface, the duct chemical environment in equally distributed host-guest interaction site and the host-guest interaction regulated and controled meticulously of superelevation, and detection performance is excellent, and can be recycled.Test paper of the present invention prepares simple and practicable, there is specific detection property and extremely low detection limit, test paper can be reused by simple processing biomarker mercaptoamino acid, can be widely applied to health detection field.
Description
Technical field
The present invention relates to Test paper fields, and in particular to one kind being based on nano molecular tong-like metal-organic framework material
(MV-MOF) preparation of the Fluorescence Increasing type test paper for biomarker analyte detection.
Background technology
The features such as test paper is low, easy to operate with its unique testing cost is widely used in every field, such as：Experiment
PH test paper, starch potassium iodide paper used in room；Temperature temperature-sensitive test paper, the wastewater recycle test paper of industry；Used in life
Blood sugar test paper etc..Since the material and method difference, the detection field and detection sensitivity of test paper that make test paper are also different.It is existing
Test paper be mostly used organic molecule and almost without specific surface nano particle make, for example, bai in 2006 etc.
(Z.Lin, S. Ou, C.Duan, B.Zhang, Z.Bai.Chem.Commun.2006,624-626.) reports use
Quinonehydrazone small molecule ruthenium complexes make test paper to detect fluorine ion.Wang in 2011 etc. (X.Yang,
E.Wang.Anal.Chem.2011,83,5005-5011. it) is detected with the metal nanoparticle of o-phenylenediamine
Copper ion and silver ion.Compared to the other materials for making test paper, molecule tong-like metal-organic framework material has its unique
Advantage, first, the specific surface of material are bigger, are more conducive to interact between Subjective and Objective, to improve the sensitivity of test paper detection.
The specific surface of molecule tong-like metal-organic framework material is up to 2000m2/ g, and traditional small molecule material and metal nanoparticle
Material does not have specific surface, even traditional porous material activated carbon also only has 800m2/g.Secondly, molecule tong-like metal is organic
The construction method of frame material is more flexible compared to other porous materials, can be directed to different detection objects, design different
Interaction sites, and the such as porous silicone zeolite of traditional material is difficult the site of modification and object interaction.Again, Molecular Tweezers
The chemical environment in shape metal-organic framework material duct is easy to regulate and control.By replacing the functional group on coordination site para postion, receive
Hydrophilic and hydrophobic, acid-base property and the electron donation in metre hole road etc. can facilitate control.It is selected by flexible modulation coordination environment
Property detection biomarker species molecule, to improve test paper detection sensitivity and biological species molecule dedicated test, and its
He does not have the metal-organic framework material of this structure or ZIF materials not to have this performance.
Invention content
The problem to be solved in the present invention is, for the deficiency of existing test paper detection, to provide a kind of based on nanometer MV-MOF's
The preparation method of Fluorescence Increasing type test paper for biomarker analyte detection, nano molecular tong-like metal used in reagent of the present invention have
Machine frame frame material is porous, can regulate and control duct coordination point chemical environment.
The purpose of the invention is achieved by the following technical solution：
The present invention for biomarker analyte detection Fluorescence Increasing type test paper based on nano molecular tong-like metal have machine frame
The preparation method of frame material, includes the following steps：By ZrCl4, TBPA, MTBC and regulation and control ligand be added in solvent, in 100-150
12-36h postcoolings are heated at DEG C, the pulverulent solids centrifuged are metal-organic framework material.Wherein, the regulation and control
Ligand includes isonicotinic acid, benzoic acid, formic acid, trifluoroacetic acid, paranitrobenzoic acid, parachlorobenzoic-acid etc., and the solvent is preferred
For N, N- diethylformamides；ZrCl4, TBPA, MTBC and regulate and control ligand molar ratio be preferably 1:0.5:0.25:15.
The preparation method of the metal-organic framework material further includes activation step, and nano molecular pincers are removed by activation
Unreacted raw material and solvent molecule in shape metal-organic framework material.The method of the activation preferably includes following steps：
The nano molecular tong-like metal-organic framework material obtained by above-mentioned preparation method is immersed into anhydrous DMAC N,N' dimethyl acetamide
In, it is exchanged 3-5 days at 80-120 DEG C, changes liquid daily 3-5 times；It is immersed in acetone, is exchanged 3-5 days at 80-120 DEG C again,
Change liquid 3-5 times daily；Then material is swapped with supercritical carbon dioxide.The tool swapped with supercritical carbon dioxide
Body method includes the following steps：Material is placed in supercritical carbon dioxide drying instrument sample room first, is added in sample room
Liquid carbon dioxide simultaneously releases carbon dioxide after keeping 0.5-1.5h, and new liquid carbon dioxide is added, and repeats this operation 3-5
It is secondary；Then the sample room that will be filled with carbon dioxide is heated to 35-40 DEG C, and releases carbon dioxide after keeping this state 0.5-1.5h
It releases, obtains the molecule tong-like metal-organic framework material of porous dry.Since material granule is smaller, it is easy to leak from sample room
Out, so needing to add an open vial to load material in sample room, add carbon dioxide and release dioxy
It is slowly operated when changing carbon in order to avoid material is boiling in vial.
A kind of preparation side for being coordinated bond material of above-mentioned nano molecular tong-like metal-organic framework material and metal ion
Method includes the following steps：Nano molecular tong-like metal-organic framework material is immersed in 24-36h in metal ion solution, is spent
Ion water washing；The metal ion includes Cu2+、Ag+Deng；The concentration of the metal ion solution is preferably 1-2mM.It should
Preparation method further includes activation step, and the method for the activation preferably includes following steps：Material after washing is immersed into nothing
It is exchanged 3-5 days in water N, N- dimethylacetylamide, changes liquid daily 3-5 times；It is immersed in acetone again, exchanges 3-5 days, change daily
Liquid 3-5 times；Then material is swapped with supercritical carbon dioxide.The specific side swapped with supercritical carbon dioxide
Method includes the following steps：Material is placed in supercritical carbon dioxide drying instrument sample room first, liquid is added in sample room
Carbon dioxide simultaneously releases carbon dioxide after keeping 0.5-1.5h, and new liquid carbon dioxide is added, and repeats this operation 3-5 times；So
The sample room that will be filled with carbon dioxide afterwards is heated to 35-40 DEG C, and releases carbon dioxide after keeping this state 0.5-1.5h
Come, obtains the nano molecular tong-like metal-organic framework material of porous dry and the coordination bond material of metal ion.
A kind of coordination bond material of nano molecular tong-like metal-organic framework material and metal ion, passes through above-mentioned preparation
Method obtains.
A kind of Fluorescence Increasing type for biomarker analyte detection based on nano molecular tong-like metal-organic framework material
Test paper, to be evenly coated with the chromatography for being coordinated bond material of above-mentioned nano molecular tong-like metal-organic framework material and metal ion
Paper.
A kind of Fluorescence Increasing type for biomarker analyte detection based on nano molecular tong-like metal-organic framework material
The preparation method of test paper, includes the following steps：Above-mentioned coordination bond material is configured to the suspension of a concentration of 10-15mM, it will
Suspension is evenly coated on chromatographic paper, and test paper is obtained after dry.
The Fluorescence Increasing type test paper can be used for the detection of biomarker, and the biomarker includes sulfydryl ammonia
Base acids marker, such as：Cysteine, homocysteine, glutathione.
The recovery method of the Fluorescence Increasing type test paper, includes the following steps：By test paper successively be immersed in deionized water,
To remove the complex that test paper inhales appended biomarker and metal ion in acetone, can be reused after dry.It is preferred that
, the time being immersed in deionized water is 24-36h, and the time being immersed in acetone is 24-48h.
The present invention has the following advantages compared with the prior art and advantageous effect：Metal organic frame used in test paper of the present invention
Material has the specific surface of superelevation, equally distributed host-guest interaction site and the host-guest interaction that regulates and controls meticulously
Duct chemical environment, detection performance is excellent, and can be recycled.Test paper of the present invention prepare it is simple and practicable, to biomarker
There is mercaptoamino acid specific detection property and extremely low detection limit, test paper can be reused by simple processing, can be wide
It is general to be applied to health detection field.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 preparation-obtained nanoscale MV-MOFs of embodiment.
Fig. 2 is with nanoscale MV-MOFs materials in embodiment 3 to the observation chart in the detection process of cysteine.In figure,
a：1.0mg materials are dispersed in 2.0mL deionized waters；b：After 1mM copper ion solutions are added dropwise；c：After 1mM cysteines are added dropwise.
Fig. 3 is the fluorescence intensity change curve graph that copper ion solution is added dropwise to original solution in embodiment 3.
Fig. 4 is the figure of fluorescence intensity changes that cysteine solution is added dropwise to original solution in embodiment 3.In figure, a：It is added dropwise half
The fluorescence intensity change curve of cystine solution；b：It is drawn as ordinate using a concentration of abscissa of cysteine, fluorescence intensity
Point diagram.
Fig. 5 is the examination criteria colorimetric card figure of double of cystine of test paper in embodiment 3, the corresponding semicystinol concentrations of a-e
Respectively 5 μM, 50 μM, 0.5mM, 5mM, 50mM.
Fig. 6 is the result figure for carrying out recycling cycle detection cysteine in embodiment 4 to test paper.In figure, a-e is respectively
Once to the result of the 5th cycle detection.
Specific implementation mode
Below by specific embodiment, the present invention is further illustrated, and its object is to help to be better understood from this hair
Bright content, but these specific embodiments are not in any way limit the scope of the present invention.
Embodiment 1
Nanoscale molecular tong-like metal-organic framework material (MV-MOFs) and metal ion (Cu2+) coordination bond material
Preparation
(1) preparation of nanoscale MV-MOFs
1) 27mg ZrCl are added in 10mL test tubes4, 30mg TBPA, 20mg MTBC, 123.0mg isonicotinic acid (or other
The regulation and control ligand of equimolar amounts) and 3.4mL N, N- diethylformamides.It is inserted into sand-bath after test tube is stoppered with rubber stopper, with
The speed of 200r/min stirs, heated at 120 DEG C postcooling for 24 hours can be obtained to room temperature, after centrifugation pulverulent solids to get to
MV-MOFs, claps scanning electron microscope such as Fig. 1, and scanning electron microscope shows that the size of MV-MOFs is 500nm or so.
The regulation and control ligand of above-mentioned equimolar amounts can also be 54.7 μ L formic acid, 107.7 μ L trifluoroacetic acids, 175.0mg benzene first
Acid, 225.5mg parachlorobenzoic-acids and 220.2mg paranitrobenzoic acids.Nanoscale MV-MOFs in following experiments and embodiment
Regulation and control ligand used is isonicotinic acid.
2) activation of nanoscale MV-MOFs
The nanoscale MV-MOFs being prepared is activated, to remove unreacted raw material and solvent molecule, method is such as
Under：Anhydrous n,N-dimethylacetamide is immersed the material into, is placed in 100 DEG C of baking ovens, N, N- dimethylacetamides are poured out after 8h or so
New n,N-dimethylacetamide is added in amine, daily in triplicate, repeats three days；It is immersed in acetone, is poured out after 8h or so again
New acetone is added in acetone, daily in triplicate, repeats three days.Then material is swapped with supercritical carbon dioxide：It is first
First material is placed in supercritical carbon dioxide drying instrument sample room, liquid carbon dioxide is added in sample room and is kept
New liquid carbon dioxide is added in the rear releasing carbon dioxide of 30min or so, repeats this operation three times；Then it will be filled with titanium dioxide
The sample room of carbon is heated to 40 DEG C, and comes out carbon dioxide slow release after keeping this state 1h, can obtain porous dry
Material.It since material granule is smaller, is easy to spill from sample room, so needing to add an open glass in sample room
Bottle loads material, add carbon dioxide and release carbon dioxide when slowly to operate in case in vial material boiling overflow
Go out.
(2) nanoscale MV-MOFs and Cu2+Coordination bond material preparation
Activated nanoscale MV-MOFs is immersed in the copper nitrate solution of 1mM for 24 hours, is then washed with deionized
Three times, washed material immerses in anhydrous n,N-dimethylacetamide, and n,N-dimethylacetamide is poured out after 8h or so, is added new
N,N-dimethylacetamide, daily in triplicate, repeat three days；It is immersed in acetone again, acetone is poured out after 8h or so, be added
New acetone repeats three days daily in triplicate.Material is swapped with supercritical carbon dioxide according still further to the above method,
Obtain activated nanoscale MV-MOFs and Cu2+Coordination bond material.
Embodiment 2
The preparation of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanoscale MV-MOFs
(1) activated nanoscale MV-MOFs and Cu in Example 12+Coordination bond material 0.36g be dispersed in 10mL
Deionized water in, be configured to 15mM coordination bond material suspension.
(2) alumina column chromatography paper is laid in glass bar of the both ends with lasso on cardboard, control thickness is 1mm, then
25 μ L of coordination bond material suspension are taken, are uniformly dropped in rubber head dropper on the chromatographic paper of 2cm × 3cm, uniform chromatography will be applied
Paper is placed on drying 24 hours at 60 DEG C, obtains the Fluorescence Increasing type for biomarker analyte detection based on nanoscale MV-MOFs
Test paper.
Embodiment 3
The detection of mercaptoamino acid
(1) make the detection of mercaptoamino acid with nanoscale MV-MOFs materials
Standard working curve is done with fluorescence titration：Instrument model used is tested in fluorescence titration：Agilent Cary
Eclipse.First, by the activated nanoscale MV-MOFs materials of 1.0mg by ultrasonic disperse in the deionized water of 2mL.Its
It is secondary, the excitation light source of 415nm is selected, under conditions of this excitation light source, is often dripped with 10 μ L and is added dropwise to the copper nitrate solution of 1mM
In original solution, record fluorescence intensity change curve is until intensity no longer declines.Then, it is often dripped half Guang of 1mM with 10 μ L
Propylhomoserin solution is added dropwise in original solution, and record fluorescence intensity change curve is until intensity no longer declines.It is dense with cysteine
Degree is abscissa, and intensity is that ordinate makees standard working curve.Observation situation in detection process is shown in Fig. 2, and it is molten that copper ion is added dropwise
The change in fluorescence curve of liquid and cysteine solution is shown in Fig. 3 and Fig. 4.
Nanoscale MV-MOFs material detection limits are calculated as, with the primary blank assay fluorescence intensity specificity of repetition ten
The three times divided by slope of a curve of coefficient, i.e.,：
The following formula of the calculating of coefficient of specificity (s),
In formula, xiIt is the fluorescence intensity surveyed each time, xnIt is surveyed average fluorescent strength.
Detection limit (cm) calculation formula it is as follows,
In formula, s is coefficient of specificity, and k is the slope that fluorescence titration restores emission lines.
Result of calculation is：S=0.0155, k=2.06 × 106M-1, cm=22.5 × 10-9M。
(2) make the detection of mercaptoamino acid with the Fluorescence Increasing type test paper based on nanoscale MV-MOFs
First make the colorimetric card of standard：Prepare one be class various concentration cysteine solution (e.g., 5 μM, 50 μM, 0.5mM,
5mM, 50mM), solution is uniformly dropped in respectively on four test paper, with ultraviolet portable light irradiation, you can see different luminous intensities
Colorimetric card (Fig. 5).The cysteine of unknown concentration is uniformly dropped on test paper, compareed with above-mentioned colorimetric card can be read it is unknown
The concentration of cysteine, the detection being with the naked eye observed that are limited to 5 μM of cysteine unknown concentration solution.
Embodiment 4
The recycling of Fluorescence Increasing type test paper based on nanoscale MV-MOFs uses
It is as follows for the recovery method of the test paper of the recycling used in circulation experiment：Test paper is immersed in deionized water first
For 24 hours, it is then immersed in acetone for 24 hours, the complex of appended biomarker and metal ion is wherein inhaled with removal, most
Drying can be reused in air afterwards.Test paper is recycled into the result that 5 times carry out 50mM cysteines cycle detection and sees figure
6, by 5 circulation and stress, the fluorescence intensity of test paper has almost no change, and detection result remains unchanged.
Embodiment 5
Fluorescence Increasing type test paper detection cysteine and other detection methods pair of the present invention based on nanoscale MV-MOFs
Than concrete outcome see the table below 1.
Table 1
NA：Document does not report data.
S1.Ros-Lis.J.；Garcia,B.；Jiménez,D.；Gonzalvo,F.；Valldecabre,
M.J.Am.Chem.Soc. 2004,126,4064.
S2.Ozoemena,K.；Westbroek,P.；Nyokong,T.Electrochem.Commun.2001,3,529.
S3.Lunar,M.；Rubio,S.；Pérez-Bendito,D.；Carreto,M.；McLeod,
C.Anal.Chim.Acta.1997, 337,341.
S4.Shang,L.；Dong,S.Biosens.Bioelecton.2009,24.1569.
S5.Han,B.；Yuan,J.；Wang,E.Anal.Chem.2009,81,5569.
S6.Salimi,A.；Pourbeyram,S.Talanta 2003,60,205.
S7.Li,T.；Shi,L.；Wang,E.；Dong,S.Chem.Eur.J.2009,15,3347.
From comparing result above can be seen that the present invention compared with other methods it is low with detection limit, be quick on the draw
Advantage；The test paper of preparation is easy to use, can be recycled.
Claims (10)
1. a kind of preparation method of the coordination bond material of nano molecular tong-like metal-organic framework material and metal ion, special
Sign is：Include the following steps：Nano molecular tong-like metal-organic framework material is immersed in 24-36h in metal ion solution,
It is washed with deionized, obtains the coordination bond material of nano molecular tong-like metal-organic framework material and metal ion.
2. preparation method according to claim 1, it is characterised in that：The metal ion includes Cu2+、Ag+；Described
A concentration of 1-2mM of metal ion solution.
3. preparation method according to claim 1 or 2, it is characterised in that：Including activation step, the method for the activation
Include the following steps：Material after washing is immersed in anhydrous n,N-dimethylacetamide and is exchanged 3-5 days, changes liquid daily 3-5 times；
It is immersed in acetone again, exchanges 3-5 days, change liquid daily 3-5 times；Then material is swapped with supercritical carbon dioxide；
Included the following steps with the method that supercritical carbon dioxide swaps：Material is placed on supercritical carbon dioxide drying instrument
In sample room, liquid carbon dioxide is added in sample room and releases carbon dioxide after keeping 0.5-1.5h, new liquid is added
Carbon dioxide repeats this operation 3-5 times；The sample room that will be filled with carbon dioxide is heated to 35-40 DEG C, and keeps this state 0.5-
Carbon dioxide is released after 1.5h.
4. preparation method according to claim 1, it is characterised in that：The nano molecular tong-like metal organic frame material
The preparation of material includes the following steps：By ZrCl4, TBPA, MTBC and regulation and control ligand be added in solvent, heated at 100-150 DEG C
12-36h postcoolings, the pulverulent solids centrifuged are nano molecular tong-like metal-organic framework material.
5. preparation method according to claim 4, it is characterised in that：The regulation and control ligand include isonicotinic acid, benzoic acid,
Formic acid, trifluoroacetic acid, paranitrobenzoic acid, parachlorobenzoic-acid etc., the solvent are N, N- diethylformamides；ZrCl4、
TBPA, MTBC and the molar ratio for regulating and controlling ligand are 1:0.5:0.25:15.
6. preparation method according to claim 4, it is characterised in that：The nano molecular tong-like metal organic frame material
The preparation of material includes activation step, and the method for the activation includes the following steps：The nano molecular tong-like gold that centrifugation is obtained
Belong to organic framework materials to immerse in anhydrous n,N-dimethylacetamide, is exchanged 3-5 days at 80-120 DEG C, change liquid daily 3-5 times；
It is immersed in acetone again, is exchanged 3-5 days at 80-120 DEG C, change liquid daily 3-5 times；Then by material supercritical carbon dioxide
It swaps.
7. a kind of Fluorescence Increasing type for biomarker analyte detection based on nano molecular tong-like metal-organic framework material tries
Paper, it is characterised in that：The test paper is to be evenly coated with to receive by what claim 1-6 any one of them preparation methods obtained
The chromatographic paper of the coordination bond material of rice molecule tong-like metal-organic framework material and metal ion.
8. the preparation method of the test paper described in claim 7, it is characterised in that：Include the following steps：Claim 1-6 will be passed through
The coordination combination material of the nano molecular tong-like metal-organic framework material that any one of them preparation method obtains and metal ion
Material is configured to the suspension of a concentration of 10-15mM, and suspension is evenly coated on chromatographic paper, and test paper is obtained after dry.
9. application of the test paper in biomarker analyte detection described in claim 7.
10. the recovery method of the test paper described in claim 7, it is characterised in that：Include the following steps：Test paper is successively immersed in
In deionized water, acetone, it can be reused after dry.
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| CN112010899B (en) * | 2020-08-17 | 2022-03-04 | 武汉大学 | Trivalent phosphine-based molecular clamp, preparation method thereof, metal-molecular clamp catalyst, preparation method and application thereof |
| CN115490869A (en) * | 2021-06-18 | 2022-12-20 | 陕西师范大学 | Method for rapidly synthesizing metal organic framework material on paper chip assisted by circular furnace |
| CN115490869B (en) * | 2021-06-18 | 2023-10-10 | 陕西师范大学 | Method for quickly synthesizing metal organic framework material on paper chip assisted by loop furnace |
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