CN106770179B - A kind of graphene oxide/molecular engram the filter membrane detecting Propranolol and its preparation and application - Google Patents
A kind of graphene oxide/molecular engram the filter membrane detecting Propranolol and its preparation and application Download PDFInfo
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- CN106770179B CN106770179B CN201710058922.1A CN201710058922A CN106770179B CN 106770179 B CN106770179 B CN 106770179B CN 201710058922 A CN201710058922 A CN 201710058922A CN 106770179 B CN106770179 B CN 106770179B
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The present invention relates to a kind of graphene oxide/molecular engram filter membrane for detecting Propranolol and its preparations and application.Specifically, the invention discloses a kind of detection methods using the content of Propranolol in graphene oxide/molecular engram filter membrane and metal nanoparticle combination Raman technology test sample.The detection method have many advantages, such as high sensitivity, it is easy to operate, time-consuming less, it is at low cost.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of graphene oxide/molecular engram mistake for detecting Propranolol
Filter membrane and its preparation and application.
Background technique
Propranolol is a kind of most common beta receptor retarding agent, for treating arrhythmia cordis, angina pectoris, high blood
The diseases such as pressure.Largely in the internal digestion of people after taking or injecting, but still there is sub-fraction to be discharged into environment, with using
The growth of amount finds the presence of Propranolol in more and more rivers, water body in lake.Propranolol, which enters human body, may occur in which entirely
Face inhibits heart function, induces and aggravates bronchial asthma, cause the adverse reactions such as intermittent claudication.
For Propranolol, currently used detection method has high performance liquid chromatography, gas chromatography-mass spectrometry etc.,
The disadvantages of generally existing processing of these methods is cumbersome, the measurement period is long, expensive equipment, it is difficult to quickly detection and real-time monitoring
Pollution variety.Therefore, people to develop quick, reliable water body Propranolol detection method have there is an urgent need to.
Summary of the invention
The purpose of the present invention is to provide one kind can highly sensitive, the easy method for rapidly and efficiently detecting Propranolol and institute
The graphene oxide that the method for stating uses/molecular engram filter membrane and its preparation and application.
The first aspect of the present invention provides a kind of detection method, and described method includes following steps:
1) graphene oxide/molecular engram filter membrane, syringe, metal nanoparticle and liquid to be checked are provided, wherein
The graphene oxide/molecular engram filter membrane include as substrate filter membrane, be incorporated into the filter membrane at least
Graphene oxide molecular engram film in one main surface；(graphene oxide and molecularly imprinted polymer form a tunic)
The syringe includes syringe body and syringe filters；
2) graphene oxide/molecular engram filter membrane is put into the syringe filters of the syringe, and
The liquid to be checked is drawn using the syringe body of the syringe；
3) assembling steps 2) gained syringe filters and syringe body, it injects so that the liquid to be checked passes through the needle
Head filter；
4) syringe filters for removing syringe obtained by step 3), are added to the syringe needle mistake for the metal nanoparticle
On the graphene oxide of filter/molecular engram filter membrane；
5) Raman spectrum detection is carried out to syringe filters obtained by step 4), is determined based on gained Raman spectrum described to be checked
The content of microsphere in liquid.
In another preferred example, the graphene oxide/molecular engram filter membrane is prepared as follows:
I) provide molecular engram pre-polymerization liquid, graphene oxide dispersion liquid, as the filter membrane of substrate, containing the molten of microsphere
Liquid and eluent for eluting microsphere；
Ii the filter membrane surface) is dispersed by the homogeneous dispersion of the graphene oxide, is filtered and optionally dry
To graphene oxide filter membrane；
Iii) the graphene oxide filter membrane is dipped in the molecular engram pre-polymerization liquid, is added containing the molten of microsphere
Liquid reacts gained mixed liquor in a nitrogen atmosphere；
Iv) optionally abovementioned steps products therefrom is carried out to wash and dry processing with solvent A；
V) abovementioned steps products therefrom is placed in eluent to the elution processing for carrying out imprint molecule, obtain the oxidation stone
Black alkene/molecular engram filter membrane.
In another preferred example, the graphene oxide/molecular engram filter membrane pore volume density is 5-30cm3/ g,
Preferably 10-25cm3/g。
In another preferred example, the molecular engram pre-polymerization liquid is prepared as follows:
A) function monomer, the first solvent, initiator and crosslinking agent are provided；
B) under agitation, the function monomer and first solvent are mixed, the first solution is obtained；
C) under agitation, first solution is added in the initiator and the crosslinking agent, obtains the molecule
Trace pre-polymerization liquid.
In another preferred example, the function monomer is selected from the group: acrylic acid, methyl methacrylate (MMA), methyl-prop
Olefin(e) acid (MAA), to vinylbenzoic acid, p -ethyl-styrene, methylene-succinic acid, or combinations thereof, be preferably selected from the following group: methyl-prop
E pioic acid methyl ester (MMA) and methacrylic acid (MAA).
In another preferred example, first solvent is selected from the group: chloroform, methanol, tetrahydrofuran, acetonitrile, or combinations thereof,
It is preferred that methanol.
In another preferred example, the initiator is selected from the group: azodiisobutyronitrile (AIBN), azobisisoheptonitrile or
A combination thereof.
In another preferred example, the crosslinking agent is selected from the group: ethylene glycol dimethacrylate (EDMA), divinyl
Benzene N, N '-methylene-bisacrylamide, glutaraldehyde, epoxychloropropane, or combinations thereof, preferred ethylene glycol dimethacrylate
(EDMA)。
In another preferred example, in the molecular engram pre-polymerization liquid, the function monomer, the initiator and the friendship
The amount ratio for joining agent is 0.001-0.1mol:0.1-1g:10-40ml, preferably 0.005-0.05mol:0.2-0.6g:15-
30ml。
In another preferred example, the decentralized medium of the dispersion liquid of the graphene oxide is water, and preferably its solid content is
2wt%~10wt%.
In another preferred example, the specific surface area of the graphene oxide is 50-1000m2/ g, preferably 100-800m2/
G, preferably 200-600m2/ g, more preferably 200-500m2/g。
In another preferred example, the filter membrane is selected from the group: nitrocellulose filter, glass fibre membrane, polyvinylidene fluoride film,
PA membrane, cellulose membrane.
In another preferred example, the microsphere is Propranolol.
In another preferred example, the component for forming the eluent is selected from the group: methanol, acetic acid, trifluoroacetic acid, three second
Amine, or combinations thereof.
In another preferred example, in step iii), before the solution containing microsphere is added, stewing process is aforementioned
Mixed liquor 5-80min obtained by step, preferably 10-60min.
In another preferred example, in step iii), the reaction time of the reaction is 1-40h, preferably 5-30h, more
Good ground 10-25h.
In another preferred example, the solvent A is selected from the group: dehydrated alcohol, methanol, ethylene glycol, or combinations thereof.
In another preferred example, in step iv), the temperature of the drying process is 20-100 DEG C, preferably 30-80
℃；And/or
The time of the drying process is 1-48h, preferably 3-30h.
In another preferred example, the time of the elution processing is 10-500min, preferably 30-400min, more preferably
50-300min。
In another preferred example, the graphene oxide molecular engram film is incorporated into two main surfaces of the filter membrane.
In another preferred example, described to be combined into physical bond or chemical bonding.
In another preferred example, described to be combined into physical bond when the filter membrane is nitrocellulose filter.
In another preferred example, described to be combined into chemical bonding when the filter membrane is glass fiber filter.
In another preferred example, group selected from the group below is contained on the surface of the graphene oxide molecular engram film: hydroxyl,
Carboxyl, epoxy group, or combinations thereof.
In another preferred example, the metal nanoparticle is the grain with (significant) surface plasma body resonant vibration property
Son.
In another preferred example, the metal nanoparticle is selected from the group: gold nanoparticle, Nano silver grain, copper nanometer
Particle or its composite nanoparticle.
In another preferred example, the partial size of the metal nanoparticle is 10-500nm, preferably 20-300nm, more preferably
30-150nm。
In another preferred example, the shape of the metal nanoparticle is selected from the group: spherical, flower-shaped, cube, it is rodlike,
Triangle, taper, or combinations thereof.
In another preferred example, in step 4), the addition quality of the metal nanoparticle is 2mg-10mg, preferably
4mg-8mg, more preferably 5mg-7mg.
In another preferred example, the method is qualitative analysis.
In another preferred example, described " determination " refers to: when gained Raman spectrum is in 1053cm-1(i.e. Propranolol molecule
Signal peak) at when having signal peak, judge to contain Propranolol molecule in the liquid to be checked；When gained Raman spectrum exists
1053cm-1When locating no signal peak, judge in the liquid to be checked without containing Propranolol molecule.
In another preferred example, the Monitoring lower-cut of the detection method is 10-10Mol/L, preferably 10-11mol/L。
The second aspect of the present invention provides a kind of graphene oxide/molecular engram filter membrane, and the filter membrane includes:
Filter membrane as substrate；
The graphene oxide molecular engram film being incorporated at least one main surface of the filter membrane.
In another preferred example, the graphene oxide molecular engram film includes molecularly imprinted polymer.
In another preferred example, the molecularly imprinted polymer is the polymer of monomer selected from the group below: acrylic acid, methyl
Methyl acrylate (MMA), methacrylic acid (MAA), to vinylbenzoic acid, p -ethyl-styrene, methylene-succinic acid or its group
It closes.
In another preferred example, the graphene oxide molecular engram film includes void structure.
In another preferred example, the pore volume density of void structure is 5- in the graphene oxide molecular engram film
30cm3/ g, preferably 10-25cm3/g。
The third aspect of the present invention provides graphene oxide/molecular engram mistake described in a kind of second aspect of the present invention
The preparation method of filter membrane, includes the following steps:
I) provide molecular engram pre-polymerization liquid, graphene oxide dispersion liquid, as the filter membrane of substrate, containing the molten of microsphere
Liquid and eluent for eluting microsphere；
Ii the filter membrane surface) is dispersed by the homogeneous dispersion of the graphene oxide, is filtered and optionally dry
To graphene oxide filter membrane；
Iii) the graphene oxide filter membrane is dipped in the molecular engram pre-polymerization liquid, is added containing the molten of microsphere
Liquid reacts gained mixed liquor in a nitrogen atmosphere；
Iv) optionally abovementioned steps products therefrom is carried out to wash and dry processing with solvent A；
V) abovementioned steps products therefrom is placed in eluent to the elution processing for carrying out imprint molecule, obtain the oxidation stone
Black alkene/molecular engram filter membrane.
The fourth aspect of the present invention, provides a kind of detection accessory, and the detection accessory includes second aspect of the present invention institute
The graphene oxide stated/molecular engram filter membrane and metal nanoparticle.
In another preferred example, the detection accessory includes:
The first component, the first component is syringe, and the syringe includes syringe body and syringe filters,
And graphene oxide described in second aspect of the present invention/molecular engram filter membrane is covered in the syringe filters；With
Second component, the second component include metal nanoparticle.
The fifth aspect of the present invention, provides a kind of detection device, and the detection device includes fourth aspect present invention institute
The detection accessory stated.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, In
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is graphene oxide of the present invention/molecular engram filter membrane preparation and application schematic diagram.
Fig. 2 is that graphene oxide/molecular engram filter membrane 1 SEM after spherical shape Ag nano particle is added dropwise in embodiment 2
Figure.
Fig. 3 is graphene oxide/molecular engram filter membrane 1 and graphene oxide/non-molecule in comparative example 1 in embodiment 1
Adsorbance of the trace filter membrane C1 to each component in the mixed solution of Propranolol, metoprolol and paracetamol.
Fig. 4 is the Raman that graphene oxide/molecular engram filter membrane 1+Ag nano particle detects Propranolol in embodiment 2
Spectrogram.
Fig. 5 is the raman spectrum that graphene oxide/molecular engram filter membrane 1 detects Propranolol in embodiment 2.
Fig. 6 is the Raman that graphene oxide/molecular engram filter membrane 2+Ag nano particle detects Propranolol in embodiment 3
Spectrogram.
Fig. 7 is the raman spectrum that graphene oxide/molecular engram filter membrane 2 detects Propranolol in embodiment 3.
Fig. 8 is that graphene oxide/molecular engram filter membrane 3+ spherical shape Au nano particle detects Propranolol in embodiment 4
Raman spectrum.
Fig. 9 is the raman spectrum that graphene oxide/molecular engram filter membrane 3 detects Propranolol in embodiment 4.
Figure 10 is that the flower-shaped Au nano particle of graphene oxide/molecular engram filter membrane 2+ detects Propranolol in embodiment 5
Raman spectrum.
Figure 11 is the raman spectrum that graphene oxide/molecular engram filter membrane 2 detects Propranolol in embodiment 5.
Figure 12 is that graphene oxide/molecular engram filter membrane 4+Ag nano particle detects Propranolol (10 in embodiment 6- 8M raman spectrum).
Figure 13 is the raman spectrum that graphene oxide/molecular engram filter membrane 4 detects Propranolol in embodiment 6.
Figure 14 is that graphene oxide/molecular engram filter membrane 4+Ag nano particle detects Propranolol (10 in embodiment 6- 11Mol/L Raman figure).
Specific embodiment
The present inventor's in-depth study by long-term prepares three layers of compound graphene oxide/molecule by substep and prints
Mark filter membrane, and it is used in combination with metal nanoparticle in injection filtration method, obtaining one kind can be highly sensitive, easy to be fast
The method of fast efficiently qualitative detection Propranolol.On this basis, inventor completes the present invention.
Term
As used herein, term " graphene oxide/molecular engram filter membrane " or " filter membrane " are used interchangeably.
Graphene oxide/molecular engram filter membrane and detection method
Molecular imprinting technology is also molecular templating techniques (MIT), is one kind with specific target molecule (template molecule, print
Score son, microsphere, branding molecule) for template, the process that there is specific selectivity to the molecule is prepared, is commonly known as made
Standby artificial " lock " technology with identification " molecule key ".It will form when template molecule (imprint molecule) is contacted with polymer monomer
Multiple action point can be memorized by this effect of polymerization process, after template molecule removal, just will form in polymer
The hole with multiple action point that shape matches is reached with template molecule space, this hole has template molecule efficient
Select evident characteristics, separation, in terms of have a wide range of applications.Molecularly imprinted polymer is primarily present absorption and holds at present
Measure relatively low disadvantage.
Graphene oxide (graphene oxide) is the derivative of graphene functionalized, and structure is similar to graphene,
For two-dimensional network structure, there is biggish specific surface area, while a large amount of oxygen-containing group and hydroxyl are contained in surface, has stronger
Reactivity makes itself and other polymerizations using its big specific surface area and active site by the modification on its surface,
Form the graphene oxide composite material to serve many purposes.
Based on this, the present invention is compound with graphene oxide by molecularly imprinted polymer, to increase adsorption site and elution mould
The quantity in the hole after plate, to improve adsorption capacity.
Surface enhanced Raman technique (SERS) is a kind of high sensitivity, quickly and effectively molecular spectrum detection technique, its energy
The finger print information of molecule is enough obtained, spectrum has high-resolution, can be realized the detection of multiple groups parts and directly detects and detect indirectly
Feature has critically important application in terms of the trace detection in the fields such as food safety, biomedicine, environmental analysis.It is fast using it
Fast sensitive, reliability detects the Propranolol in water body, can effectively monitor in real time and the pollution feelings in early warning water
Condition has important scientific meaning and economic results in society.
Based on this, the present invention provides a kind of graphene oxide/molecular engram filter membranes, and the filter membrane includes:
Filter membrane as substrate；
The graphene oxide molecular engram film being incorporated at least one main surface of the filter membrane.
In the present invention, the graphene oxide molecular engram film includes molecularly imprinted polymer.
In another preferred example, the molecularly imprinted polymer is selected from the poly- of the monomer for including (but being not limited to) the following group
Close object: acrylic acid, methyl methacrylate (MMA), methacrylic acid (MAA), to vinylbenzoic acid, p -ethyl-styrene, Asia
Dimethyl succinic acid, or combinations thereof.
In another preferred example, the graphene oxide molecular engram film includes void structure.
In another preferred example, the pore volume density of void structure is 5- in the graphene oxide molecular engram film
30cm3/ g, preferably 10-25cm3/g。
Further, the present invention provides a kind of detection method, described method includes following steps:
1) graphene oxide/molecular engram filter membrane, syringe, metal nanoparticle and liquid to be checked are provided, wherein
The graphene oxide/molecular engram filter membrane include as substrate filter membrane, be incorporated into the filter membrane at least
Graphene oxide molecular engram film in one main surface；
The syringe includes syringe body and syringe filters；
2) graphene oxide/molecular engram filter membrane is put into the syringe filters of the syringe, and
The liquid to be checked is drawn using the syringe body of the syringe；
3) assembling steps 2) gained syringe filters and syringe body, it injects so that the liquid to be checked passes through the needle
Head filter；
4) syringe filters for removing syringe obtained by step 3), are added to the syringe needle mistake for the metal nanoparticle
On the graphene oxide of filter/molecular engram filter membrane；
5) Raman spectrum detection is carried out to syringe filters obtained by step 4), is determined based on gained Raman spectrum described to be checked
The content of microsphere in liquid.
In the present invention, the graphene oxide/molecular engram filter membrane is prepared as follows:
I) provide molecular engram pre-polymerization liquid, graphene oxide dispersion liquid, as the filter membrane of substrate, containing the molten of microsphere
Liquid and eluent for eluting microsphere；
Ii the filter membrane surface) is dispersed by the homogeneous dispersion of the graphene oxide, is filtered and optionally dry
To graphene oxide filter membrane；
Iii) the graphene oxide filter membrane is dipped in the molecular engram pre-polymerization liquid, is added containing the molten of microsphere
Liquid reacts gained mixed liquor in a nitrogen atmosphere；
Iv) optionally abovementioned steps products therefrom is carried out to wash and dry processing with solvent A；
V) abovementioned steps products therefrom is placed in eluent to the elution processing for carrying out imprint molecule, obtain the oxidation stone
Black alkene/molecular engram filter membrane.
In another preferred example, the graphene oxide/molecular engram filter membrane pore volume density is 5-30cm3/ g,
Preferably 10-25cm3/g。
In another preferred example, the molecular engram pre-polymerization liquid is prepared as follows:
A) function monomer, the first solvent, initiator and crosslinking agent are provided；
B) under agitation, the function monomer and first solvent are mixed, the first solution is obtained；
C) under agitation, first solution is added in the initiator and the crosslinking agent, obtains the molecule
Trace pre-polymerization liquid.
In another preferred example, the function monomer includes (but being not limited to): acrylic acid, methyl methacrylate
(MMA), methacrylic acid (MAA), to vinylbenzoic acid, p -ethyl-styrene, methylene-succinic acid, or combinations thereof, preferably select
From the following group: methyl methacrylate (MMA) and methacrylic acid (MAA).
In another preferred example, first solvent include (but being not limited to): chloroform, methanol, tetrahydrofuran, acetonitrile,
Or combinations thereof, preferred methanol.
In another preferred example, the initiator includes (but being not limited to): azodiisobutyronitrile (AIBN), azo two are different
Heptonitrile, or combinations thereof.
In another preferred example, the crosslinking agent includes (but being not limited to): ethylene glycol dimethacrylate (EDMA),
Divinylbenzene N, N '-methylene-bisacrylamide, glutaraldehyde, epoxychloropropane, or combinations thereof, preferred ethylene glycol dimethyl third
Olefin(e) acid ester (EDMA).
In another preferred example, in the molecular engram pre-polymerization liquid, the function monomer, the initiator and the friendship
The amount ratio for joining agent is 0.001-0.1mol:0.1-1g:10-40ml, preferably 0.005-0.05mol:0.2-0.6g:15-
30ml。
In another preferred example, the decentralized medium of the dispersion liquid of the graphene oxide is water, and preferably its solid content is
2wt%~10wt%.
In another preferred example, the specific surface area of the graphene oxide is 50-1000m2/ g, preferably 100-800m2/
G, preferably 200-600m2/ g, more preferably 200-500m2/g。
In another preferred example, the filter membrane includes (but being not limited to): nitrocellulose filter, gathers partially glass fibre membrane
Fluoride film, PA membrane, cellulose membrane.
In another preferred example, the microsphere is Propranolol.
In another preferred example, the component for forming the eluent includes (but being not limited to): methanol, acetic acid, trifluoro second
Acid, triethylamine, or combinations thereof.
In another preferred example, in step iii), before the solution containing microsphere is added, stewing process is aforementioned
Mixed liquor 5-80min obtained by step, preferably 10-60min.
In another preferred example, in step iii), the reaction time of the reaction is 1-40h, preferably 5-30h, more
Good ground 10-25h.
In another preferred example, the solvent A includes (but being not limited to): dehydrated alcohol, methanol, ethylene glycol or its group
It closes.
In another preferred example, in step iv), the temperature of the drying process is 20-100 DEG C, preferably 30-80
℃；And/or
The time of the drying process is 1-48h, preferably 3-30h.
In another preferred example, the time of the elution processing is 10-500min, preferably 30-400min, more preferably
50-300min。
In another preferred example, the graphene oxide molecular engram film is incorporated into two main surfaces of the filter membrane.
In another preferred example, described to be combined into physical bond or chemical bonding.
In another preferred example, described to be combined into physical bond when the filter membrane is nitrocellulose filter.
In another preferred example, described to be combined into chemical bonding when the filter membrane is glass fiber filter.
In another preferred example, the surface of the graphene oxide molecular engram film is contained selected from including (but being not limited to)
The group of the following group: hydroxyl, carboxyl, epoxy group, or combinations thereof.
In the present invention, the metal nanoparticle is the particle with (significant) surface plasma body resonant vibration property.
In another preferred example, the metal nanoparticle includes (but being not limited to): gold nanoparticle, nano grain of silver
Son, copper nano-particle or its composite nanoparticle.
In another preferred example, the partial size of the metal nanoparticle is 10-500nm, preferably 20-300nm, more preferably
30-150nm。
In another preferred example, the shape of the metal nanoparticle include (but being not limited to): it is spherical, flower-shaped, cube
Body, rodlike, triangle, taper, or combinations thereof.
In another preferred example, in step 4), the addition quality of the metal nanoparticle is 2mg-10mg, preferably
4mg-8mg, more preferably 5mg-7mg.
In the present invention, the method is qualitative analysis.
In another preferred example, described " determination " refers to: when gained Raman spectrum is in 1053cm-1(i.e. Propranolol molecule
Signal peak) at when having signal peak, judge to contain Propranolol molecule in the liquid to be checked；When gained Raman spectrum exists
1053cm-1When locating no signal peak, judge in the liquid to be checked without containing Propranolol molecule.
In the present invention, the Monitoring lower-cut of the detection method is 10-10Mol/L, preferably 10-11mol/L。
To sum up, in the present invention, by growing graphene oxide and molecularly imprinted polymer on filter membrane, oxidation stone is formed
Black alkene/molecular engram filter membrane realizes the selective enrichment to Propranolol, and using with the active metal nano of SERS
Particle provides signal enhancing, in conjunction with injection filtration method detection process more fast and convenient for operation.
Preparation method
The present invention also provides the graphene oxide described in one kind/molecular engram filter membrane preparation method, including it is as follows
Step:
I) provide molecular engram pre-polymerization liquid, graphene oxide dispersion liquid, as the filter membrane of substrate, containing the molten of microsphere
Liquid and eluent for eluting microsphere；
Ii the filter membrane surface) is dispersed by the homogeneous dispersion of the graphene oxide, is filtered and optionally dry
To graphene oxide filter membrane；
Iii) the graphene oxide filter membrane is dipped in the molecular engram pre-polymerization liquid, is added containing the molten of microsphere
Liquid reacts gained mixed liquor in a nitrogen atmosphere；
Iv) optionally abovementioned steps products therefrom is carried out to wash and dry processing with solvent A；
V) abovementioned steps products therefrom is placed in eluent to the elution processing for carrying out imprint molecule, obtain the oxidation stone
Black alkene/molecular engram filter membrane.
Using
The present invention also provides a kind of detection accessory, the detection accessory includes the graphene oxide/molecular engram
Filter membrane and metal nanoparticle.
In another preferred example, the detection accessory includes:
The first component, the first component is syringe, and the syringe includes syringe body and syringe filters,
And graphene oxide/molecular engram the filter membrane is covered in the syringe filters；With
Second component, the second component include metal nanoparticle.
The present invention also provides a kind of detection device, the detection device includes the detection accessory.
Compared with prior art, the present invention has following major advantage:
(1) graphene oxide/molecular engram filter membrane selectivity is good, and adsorption capacity is high, to the Propranolol in water body
With excellent accumulation ability；
(2) injection filtration method is easy to operate, and enrichment rate is fast, shortens entire detection time；
(3) metal nanoparticle being added dropwise is in filter membrane surface, and incident light is unobstructed, and signal is good；
(4) the detection method applicability is wider, easy to operate, and sensitivity is good.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
The preparation of 1 graphene oxide of embodiment/molecular engram filter membrane 1
1) methyl methacrylate of the 0.2M of 50mL is dissolved in the methanol solution of 50mL first, uniform stirring
10min is slowly added to 0.4g azodiisobutyronitrile and the ethylene glycol dimethacrylate of 20mL during stirring, after
Continuous stirring 10min, obtains molecular engram pre-polymerization liquid 1.
2) use nitrocellulose filter as substrate, by graphene oxide dispersion that 3mL concentration is 1mg/mL (admittedly contain
Amount 2%, the specific surface area 200m of graphene oxide2/ g) it is uniformly dispersed on the filter membrane, after being filtered by vacuum on the filter
Dry a whole night obtains graphene oxide filter membrane 1 in air, cleans before every use using deionized water.
3) graphene oxide filter membrane 1 made from step 2) is immersed in the molecular engram pre-polymerization of 120mL made from step 1
In liquid, after standing 30min, the Propranolol that 20mL concentration is 10mM is added, is reacted 24 hours under the protection of nitrogen, reaction stops
It is used washes of absolute alcohol 4 times after only, filter membrane is put in drying 24 hours in 40 DEG C of vacuum oven later, is finally placed it in
(9:1/ volume: volume) is impregnated 1 hour in methanol/acetic acid mixed solution, obtains graphene oxide/molecular engram filter membrane 1.
1 graphene oxide of comparative example/non-molecular engram filter membrane C1 preparation
With embodiment 1, difference is: imprint molecule Propranolol is added without during preparation.
Fig. 3 is graphene oxide/molecular engram filter membrane 1 and graphene oxide/non-molecule in comparative example 1 in embodiment 1
(each component concentration is 10 to mixed solution of the trace filter membrane C1 to Propranolol, metoprolol and paracetamol-4M each group in)
The adsorbance divided.
As can be seen from Figure 3: graphene oxide/molecular engram filter membrane 1 is much larger than it to the adsorbance of Propranolol
His two kinds of substances, equally also above graphene oxide/non-molecular engram filter membrane C1 of Propranolol is not added to Propranolol
Absorption illustrates that graphene oxide described in embodiment 1/molecular engram filter membrane 1 has good selective absorption to Propranolol
(specific adsorption).
Further calculated, graphene oxide described in embodiment 1/molecular engram filter membrane 1 pore volume density is
16.29cm3/g。
Embodiment 2 detects Propranolol
The preparation of Ag nano particle
By 20mL silver nitrate solution (10-2M), citric acid three sodium solution and 80mL deionization that 20mL mass fraction is 1%
Water is uniformly mixed, and the sodium borohydride solution (10 of 100mL Fresh is added under conditions of strong mixing-2M), continue at room temperature
1h is reacted, the spherical Ag nano particle colloidal sol of yellow green, granular size 40-70nm are obtained.
Graphene oxide/molecular engram filter membrane 1+Ag nano particle detects Propranolol
Graphene oxide/molecular engram filter membrane 1 is put into syringe filters；Syringe draws 2mL, 10-7The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, are added dropwise on it
Spherical Ag nano particle obtained by 0.5mL above-mentioned steps carries out Raman spectrum detection, obtains enhanced raman spectrum, see
Fig. 4.
Fig. 2 is that graphene oxide/molecular engram filter membrane 1 SEM after spherical shape Ag nano particle is added dropwise in embodiment 2
Figure.
As can be seen from Figure 2: Ag nano particle is dispersed on graphene oxide/molecular engram filter membrane, graphene oxide
Containing a large amount of fold, thus it can provide more binding sites in favor of the absorption of template molecule.
Graphene oxide/molecular engram filter membrane 1 detects Propranolol
Graphene oxide/molecular engram filter membrane 1 is put into syringe filters；Syringe draws 2mL, 10-7The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, directly progress Raman light
Spectrum detection, obtains raman spectrum, sees Fig. 5.
Relative to Fig. 5, Fig. 4 is 1053cm in Raman shift-1Place can see the Raman signal peak of Propranolol molecule.
Embodiment 3 detects Propranolol
The preparation of graphene oxide/molecular engram filter membrane 2
1) methacrylic acid of the 0.2M of 50mL is dissolved in the methanol solution of 50mL first, uniform stirring 20min, In
During stirring, it is slowly added to 0.4g azodiisobutyronitrile and the ethylene glycol dimethacrylate of 20mL, continues to stir
10min obtains molecular engram pre-polymerization liquid 2.
Step 2) -3) it is same as Example 1.
Further calculated, graphene oxide described in embodiment 3/molecular engram filter membrane 3 pore volume density is
17.12cm3/g。
The preparation of Ag nano particle is the same as embodiment 2.
Graphene oxide/molecular engram filter membrane 2+Ag nano particle detects Propranolol
Graphene oxide/molecular engram filter membrane 2 is put into syringe filters；Syringe draws 2mL, 10-5The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, 1mL is added dropwise on it
Spherical Ag nano particle obtained by above-mentioned steps carries out Raman spectrum detection, obtains enhanced raman spectrum, see Fig. 6.
Graphene oxide/molecular engram filter membrane 2 detects Propranolol
Graphene oxide/molecular engram filter membrane 2 is put into syringe filters；Syringe draws 2mL, 10-5The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, directly progress Raman light
Spectrum detection, obtains raman spectrum, sees Fig. 7.
Relative to Fig. 7, Fig. 6 is 1053cm in Raman shift-1Place can see the Raman signal peak of Propranolol molecule.
Embodiment 4 detects Propranolol
The preparation of graphene oxide/molecular engram filter membrane 3
Step 1) -2) it is same as Example 1.
3) molecular engram for graphene oxide filter membrane 3 made from step 2) being immersed in 120mL made from step 1) is pre-
In poly- liquid 1, after standing 30min, the Propranolol that 20mL concentration is 10mM is added, reacts 24 hours under the protection of nitrogen, instead
It is used washes of absolute alcohol 4 times after should stopping, gained filter membrane is put in drying 24 hours in 60 DEG C of vacuum oven later, finally
Place it in methanol/acetic acid mixed solution in (9:1/ volume: volume) and impregnate 3 hours, thus obtain graphene oxide/point
Sub- trace filter membrane 3.
Further calculated, graphene oxide described in embodiment 4/molecular engram filter membrane 3 pore volume density is
18.3cm3/g。
The preparation of spherical Au nano particle
The sodium citrate aqueous solution that 150mL concentration is 2% is added in 250mL three neck round bottom flask, in 120 DEG C of oil baths
In be heated to boiling, under magnetic stirring speed, rapidly join the HAuCl of 1mL 25mM4Aqueous solution continues heating stirring about
10min；When solution colour becomes claret, solution temperature is down to 90 DEG C of constant temperature, 1mL is added under magnetic stirring speed
25mM HAuCl4Aqueous solution reacts 30min with this condition, repeats the step twice.It is kept away to solution cooled to room temperature
Light, 0~4 DEG C saves for use.
Through calculating, the partial size of gained spherical shape Au nano particle is about 60nm.
Graphene oxide/molecular engram filter membrane 3+ spherical shape Au nano particle detects Propranolol
Graphene oxide/molecular engram filter membrane 3 is put into syringe filters；Syringe draws 2mL, 10-6The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, 1mL is added dropwise on it
Spherical Au nano particle obtained by above-mentioned steps carries out Raman spectrum detection, obtains enhanced raman spectrum, see Fig. 8.
Graphene oxide/molecular engram filter membrane 3 detects Propranolol
Graphene oxide/molecular engram filter membrane 3 is put into syringe filters；Syringe draws 2mL, 10-6The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, directly progress Raman light
Spectrum detection, obtains raman spectrum, sees Fig. 9.
Relative to Fig. 9, Fig. 8 is 1053cm in Raman shift-1Place can see the Raman signal peak of Propranolol molecule.
Embodiment 5 detects Propranolol
The preparation of flower-shaped Au nano particle
By 2ml HAuCl4(24mM) solution is added in 4ml PDDA (35wt%) solution, and 15min is stirred at room temperature,
Freshly prepared 5ml ascorbic acid (0.1M) is rapidly joined and is vigorously stirred 30s, so that it becomes it is colourless, then by above-mentioned step
Rapid spherical shape Au nanoparticles solution obtained is added thereto as seed solution, continues to stir 30s.4 hours are stood at room temperature,
Then 9000rpm is centrifuged 10 minutes, obtains flower-shaped Au nano particle.
Through calculating, the partial size of the flower-shaped Au nano particle is about 100nm.
The flower-shaped Au nano particle of graphene oxide/molecular engram filter membrane 2+ detects Propranolol
Graphene oxide/molecular engram filter membrane 2 is put into syringe filters；Syringe draws 1.5mL, 10-7M's is general
Naphthalene Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, are added dropwise on it
Flower-shape Au nano particle obtained by 0.4mL above-mentioned steps carries out Raman spectrum detection, obtains enhanced raman spectrum, see
Figure 10.
Graphene oxide/molecular engram filter membrane 2 detects Propranolol
Graphene oxide/molecular engram filter membrane 2 is put into syringe filters；Syringe draws 1.5mL, 10-7M's is general
Naphthalene Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, directly progress Raman
Spectral detection obtains raman spectrum, sees Figure 11.
Relative to Figure 11, Figure 10 is 1053cm in Raman shift-1Place can see the Raman signal peak of Propranolol molecule.
Embodiment 6 detects Propranolol
The preparation of graphene oxide/molecular engram filter membrane 4
Step 1) and 3) same as Example 1.
2) use glass fiber filter as substrate, graphene oxide (solid content 5%, the oxygen for being 3mg/mL by 3mL concentration
The specific surface area 500m of graphite alkene2/ g) solution is uniformly dispersed on filter membrane, after being filtered by vacuum on the filter in air
Dry a whole night obtains graphene oxide filter membrane 4, cleans before every use using deionized water.
Further calculated, graphene oxide described in embodiment 6/molecular engram filter membrane 4 pore volume density is
15.7cm3/g。
The preparation of Ag nano particle is the same as embodiment 2.
Graphene oxide/molecular engram filter membrane 4+Ag nano particle detects Propranolol
Graphene oxide/molecular engram filter membrane 4 is put into syringe filters；Syringe draws 2mL, 10-8The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, are added dropwise on it
Spherical Ag nano particle obtained by 0.5mL above-mentioned steps carries out Raman spectrum detection, obtains enhanced raman spectrum, see
Figure 12.
Graphene oxide/molecular engram filter membrane 4 detects Propranolol
Graphene oxide/molecular engram filter membrane 4 is put into syringe filters；Syringe draws 2mL, 10-8The general naphthalene of M
Luo Er solution puts on syringe filters injection filtering Propranolol solution；Then syringe filters are removed, directly progress Raman light
Spectrum detection, obtains raman spectrum, sees Figure 13.
Relative to Figure 13, Figure 12 is 1053cm in Raman shift-1Place can see the Raman signal peak of Propranolol molecule.
Monitoring lower-cut
Further, according to the method described above by various concentration (10-9mol/L、10-10mol/L、10-11mol/L、10-12mol/
L Propranolol solution) is detected, and the lower limit of its detection is found, and obtaining concentration is 10-11Mol/L is that the method detection is general
The detectable limit of naphthalene Luo Er, testing result are shown in Figure 14.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (7)
1. a kind of method for detecting Propranolol, which is characterized in that described method includes following steps:
1) graphene oxide/molecular engram filter membrane, syringe, metal nanoparticle and liquid to be checked are provided, wherein
The graphene oxide/molecular engram filter membrane include as substrate filter membrane, be incorporated into the filter membrane at least one
Graphene oxide molecular engram film in main surface；
The syringe includes syringe body and syringe filters；
2) graphene oxide/molecular engram filter membrane is put into the syringe filters of the syringe, and used
The syringe body of the syringe draws the liquid to be checked；
3) assembling steps 2) gained syringe filters and syringe body, it injects so that the liquid to be checked passes through the syringe needle mistake
Filter；
4) syringe filters for removing syringe obtained by step 3), are added to the syringe filters for the metal nanoparticle
Graphene oxide/molecular engram filter membrane on；
5) Raman spectrum detection is carried out to syringe filters obtained by step 4), the liquid to be checked is determined based on gained Raman spectrum
The content of middle microsphere；
The microsphere is Propranolol.
2. the method as described in claim 1, which is characterized in that the graphene oxide/molecular engram filter membrane is to make as follows
Standby:
I) provide molecular engram pre-polymerization liquid, the dispersion liquid of graphene oxide, the filter membrane as substrate, the solution containing microsphere and
For eluting the eluent of microsphere；
Ii the filter membrane surface) is dispersed by the homogeneous dispersion of the graphene oxide, suction filtration obtains graphene oxide filtering
Film；
Iii) the graphene oxide filter membrane is dipped in the molecular engram pre-polymerization liquid, the solution containing microsphere is added,
Gained mixed liquor is reacted in a nitrogen atmosphere；
V) abovementioned steps products therefrom is placed in eluent to the elution processing for carrying out imprint molecule, obtain the graphite oxide
Alkene/molecular engram filter membrane.
3. the method as described in claim 1, which is characterized in that the metal nanoparticle is with surface plasma body resonant vibration
The particle of property.
4. the method as described in claim 1, which is characterized in that the method is qualitative analysis.
5. the method as described in claim 1, which is characterized in that the Monitoring lower-cut of the detection method is 10-10mol/L。
6. method according to claim 2, which is characterized in that the step ii) in, graphite oxide is dried to obtain after suction filtration
Alkene filter membrane.
7. method according to claim 2, which is characterized in that in the step iii) and the step v) between have
Step iv) abovementioned steps products therefrom is carried out to wash and dry processing with solvent A；The solvent A is selected from the group: anhydrous second
Alcohol, methanol, ethylene glycol, or combinations thereof.
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| Combination of solid phase extraction and surface-enhanced Raman spectroscopy for rapid analysis;Yongchao Lai et al.;《Analyst》;20130507;第2599页左栏倒数第1段-第2601页左栏倒数第2段 * |
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