CN109580583A - A kind of dense form Raman spectrum base and the preparation method and application thereof - Google Patents
A kind of dense form Raman spectrum base and the preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00206—Processes for functionalising a surface, e.g. provide the surface with specific mechanical, chemical or biological properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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
- G01N21/65—Raman scattering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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
- G01N21/65—Raman scattering
- G01N2021/653—Coherent methods [CARS]
- G01N2021/655—Stimulated Raman
Abstract
The invention discloses a kind of dense form Raman spectrum base and the preparation method and application thereof, the substrate include glass slide, modification in glass slide polymethyl siloxane (PDMS) coating, be covered on coating by hollow magnetic ZnO/ZnFe2O4The coffee spot deposit with certain thickness densification of@Ag nano particle composition, to obtain the active substrate with surface-enhanced Raman effects；The substrate passes through preparation enhancing Raman active material, glass slide cleaning, polymethyl siloxane (PDMS) modification, the deposition of Raman active material and etc. acquisition, using magnetic field effect and the method for coffee ring effect self assembly deposition is inhibited to prepare substrate, this method have it is convenient and simple, it is low in cost, it is easy to accomplish the advantages that.By the substrate be used for bacillus anthracis marker SERS detection, detection sensitivity and stability with higher, in the case where being not directly contacted with bacterium source can effective monitoring and analysis bacillus anthracis, in environment, there is very huge application prospect in the fields such as medical treatment.
Description
Technical field
The invention belongs to LR laser raman detection technique field, in particular to a kind of dense form enhancing raman spectrum substrate preparation
Method and its application.
Background technique
Bacillus anthracis (Bacillus anthracis) is bacillus, is that Grain-positive bacillus is a kind of, is nature epidemic disease
Source property and Zoonosis infect the pathogen of anthracnose, and in normal circumstances, bacillus anthracis will form " gemma ", and gemma is easy
It is infected by approach such as respiratory tract, skins, vitality is extremely indomitable, can resist various harsh environments, and can deposit for a long time
It is living, still there is very strong pathogenecity after buried, vacuum preservation decades, can be used as the raw material of chemical and biological weapons.Seriously
Threaten human health and social safety.Although current medical level achieves the development advanced by leaps and bounds, society faces this
When dangerous sexually transmitted disease, there is no full reply means.Traditional detection Bacillus anthracis means have polymerase chain at present
Reaction, cytomorphology, enzyme linked immunoassay, but generally existing detection cycle is long, and do not have the real-time detection at scene
Condition lacks live quick diagnosis in epidemic situation development.Therefore it is badly in need of developing a kind of detection method of convenient and efficient, to anthrax
Bacillus is monitored and analyzes.Pyridinedicarboxylic acid (DPA, pyridine -2,6- dicarboxylic acids) is the main component of bacterial spore, it accounts for spore
The 5-15% of sub- dry mass.Therefore, DPA can be used as effective biomarker of anthracnose, and detection DPA is dense in anthracnose detection
Degree is of great significance.Detecting common method to DPA at present has gas chromatography-mass spectrum (GC-MS), electrochemical process, liquid phase color
Compose (HPLC) fluorescent spectrometry etc., although such method DPA can be carried out it is accurate qualitative and quantitative, when its pre-processing
Between it is long, stability and specificity are poor, and detection technique means are cumbersome, are badly in need of developing in view of the above circumstances a kind of convenient and efficient
And efficient detection method, bacillus anthracis marker DPA is monitored and is analyzed.
In recent decades, Surface enhanced Raman spectroscopy (SERS) technology is with spies such as its hypersensitive, non-destructive, quick responses
Point is widely used in fields such as chemistry, physics, material science, pharmacy and bio-sensings.Especially it is such as high noise
Than, excite without photobleaching and using Single wavelength the advantages that so that SERS becomes offline and on-line checking biological and chemical substance
Power analysis tool.For SERS phenomenon, there are two types of enhancing mechanism to be accepted extensively by researchers, Electromagnetic enhancement (EM) and change
Enhancing (CM) is learned, wherein Electromagnetic enhancement is the electron interaction in incident electric fields and metal surface as a result, leading to metal watch
Surface plasma excitation, to enhance the electric field of metal surface.It is roughened nanostructure on metal surface and is conducive to Electromagnetic enhancement,
Roughened Raman substrate can be built by assembling design.Chemical enhancement is attributed between the molecule of absorption and noble metal structures
Charge interaction.People are almost it is believed that Electromagnetic enhancement is the most important of the SERS phenomenon observed in conductive material
Contribution.To semiconductor-noble metal nano composite material, researches show that the great potentials of Chemical enhancement out recently.Most of SERS
Substrate and noble metal structures (Au, Ag and Cu) are compound, and noble metal structures are various shapes, for example, nanometer sheet, nano wire, nanometer
Ball etc..Some researches show that the semi-conductor nano particles of composite noble metal to have SERS humidification, due to Electromagnetic enhancement and half
Bigger Raman enhancing may be implemented in the composite material of the effect of conductor induced chemical enhancing, semiconductor and noble metal.
ZnO is the general semiconductor material that a kind of direct band gap is 3.37 eV, due to as SERS substrate in Chemical enhancement
The excellent properties of aspect and paid special attention to.It is multiple to prepare this novel ZnO/ noble metal that researchers develop certain methods
Condensation material SERS substrate.For example, Ag nanoparticle (Ag-NPs) is assembled into ZnO nanorod (ZnO-NRs) using electroless plating method
Surface, however the spatial joint clearance on ZnO carrier between noble metal granule is too big and cannot be effective as SERS " hot spot " work,
And the coupling agent of synthesis addition complexity can bring volume in SERS measurement for being connected to ZnO and noble metal nano particles
Outer Raman signal, especially if target analytes have the raman spectral signal similar with coupling agent.In order to solve this
Problem develops physical sputtering method.For example, Ag nanocluster is deposited to by using air accumulation type nanocluster light beam source
3D Ag-ZnO SERS substrate is prepared on ZnO nanowire array.However, these methods generally require cumbersome synthesis step,
Expensive accurate instrument, higher operating technology etc. require, inadaptable quickly and easily to prepare SERS substrate.
When fixed drop is fixed on a solid surface, evaporation can cause outside Capillary Flow, make to suspend
Grain is mobile to the periphery of drop and leaves cyclic structure.It is aspherical compared with being carried to contact line and forming the spheric granules of ring
Particle tends at air-water interface be adhering to each other, they obtain the resistance to Capillary Flow and the suppression of enhancing there
Coffee ring effect processed, while externally-applied magnetic field can also promote to inhibit the effect of coffee ring.
Summary of the invention
The object of the present invention is to provide one kind based on Raman spectrum base and the preparation method and application thereof, with suppression
Coffee ring effect processed and magnetic field control self assembly densification coffee spot substrate, propose that one kind is simple and convenient, inexpensive, stability is good
The substrate of the preparation method of active Raman substrate, preparation can be used directly, can be stored for a long time in air, and activity is still
It can keep.The substrate of preparation had not only had Chemical enhancement effect but also had had Electromagnetic enhancement effect, reduced surface enhanced Raman substrate
The problem of dosage of noble metal and its stability, solves high cost and complicated large-scale instrument, it is difficult to realize low concentration
Quickly detection etc. presently, there are detection problem, in environment, there is very huge application prospect in the fields such as medical treatment.
Realizing the specific technical solution of the object of the invention is:
A kind of dense form Raman spectrum base, the substrate include glass slide, are modified in the poly- methyl of glass slide
Siloxanes (PDMS) coating, be covered on coating by hollow magnetic ZnO/ZnFe2O4Having for@Ag nano particle composition is certain thick
Fine and close coffee spot deposit is spent, to obtain the active substrate with surface-enhanced Raman effects；The substrate is increased by preparation
Hale graceful active material, glass slide cleaning, polymethyl siloxane (PDMS) modification, the deposition of Raman active material and etc. obtain
, using magnetic field effect and the method for coffee ring effect self assembly deposition is inhibited to prepare substrate, method, which has, facilitates letter
It is single, it is low in cost, it is easy to accomplish and sample treatment it is simple the advantages that.The substrate is used for the SERS inspection of bacillus anthracis marker
It surveys, detection sensitivity and stability with higher, it can effective monitoring and analysis charcoal in the case where being not directly contacted with bacterium source
Subcutaneous ulcer bacillus, in environment, there is very huge application prospect in the fields such as medical treatment.
A kind of preparation method of dense form Raman spectrum base, this method comprising the following specific steps
Step 1: the glass slide or silicon wafer of cleaning deposition Raman-active species
Glass slide having a size of (1~3) cm X (1~3) cm or silicon wafer will be cut into and first wash surface dirt with detergent
Then dirt, then wash detergent with clear water impregnates ten minutes with reagent to remove its oxide on surface, then with acetone, alcohol
20~40 min of each ultrasonic cleaning, last deionized water are cleaned by ultrasonic 30~50 min, and taking-up is put into 50~70 DEG C of baking ovens
It is dried for standby；The reagent is the HF of 10~30 % of concentration, one of the NaOH of 5~20 % of concentration and Piranha solution or several
Kind mixing；Wherein, the Piranha solution is the mixed solution of the concentrated sulfuric acid and 30% hydrogen peroxide with volume for 7:3；
Step 2: modification polymethyl siloxane (PDMS) is in glass slide or silicon wafer
Polymethyl siloxane (PDMS) prepolymer is uniformly mixed with curing agent with 10~12:1 of mass ratio, it is dry to be then placed in vacuum
It is deaerated after 20~40 min in dry case, it is uniformly spun on glass slide or silicon chip surface with equal glue machine, is placed in baking oven
Solidification, solidification temperature are 80~120 DEG C, and curing time is 20~40 min；Solidification terminate take out be cooled to room temperature be placed on it is dry
Net deposit storage box is spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOF presoma is prepared
First under magnetic stirring by Zn (NO3)2﹒ 6H2O and Fe (acac)3It is dissolved in oil phase solvent DMF and aqueous phase solvent ethyl alcohol
In mixed solution；Then, by terephthalic acid (TPA) (C6H4(COOH)2) and PVP(K30, Mw=40,000) add under violent stirring
Enter into the mixed solution, be placed in the stainless steel sealing container of teflon lined, and heating 18 is small at 180 DEG C
When；It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing for several times；By product dry 24 at 80 DEG C
H, and it is expressed as Zn/Fe-MOFs；Wherein, Zn (NO3)2﹒ 6H2O、Fe(acac)3、C6H4(COOH)2, PVP molar ratio are as follows: 3.5
~5: 1~2: 0.5~1: 2 X 10-6~4 X 10-6, DMF used and ethyl alcohol as reaction dissolvent, the oil phase solvent be DMF,
NMP or DMSO, the aqueous phase solvent are ethyl alcohol, acetone or tetrahydrofuran；Wherein, the volume ratio of oil phase solvent and aqueous phase solvent
Are as follows: 2~4: 2~1；Reaction temperature used is 150~200 DEG C, and the reaction time is 15~24 h；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat, rate be 2 DEG C/
Min, calcines 3~5 h, is cooled to room temperature after the completion of calcining, is classified spherical shape ZnO/ZnFe to obtain2O4Hollow nanometer bouquet；Tubular type
Furnace calcination temperature is 500~700 DEG C, and heating rate is 1~5 DEG C/min；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
100 mg ZnO/ZnFe has been synthesized into2O4Hollow nanometer bouquet is added to containing in 50 mL ethylene glycol round-bottomed flasks；Then
Round-bottomed flask is placed in oil bath and is heated to 120 DEG C；After keeping 1 h of temperature at 120 DEG C, 40 mg are added into suspension
AgNO3, go forward side by side 3 h of single step reaction；After cooled to room temperature, by the way that product is collected by centrifugation and is washed with deionized three
It is secondary, product is dried into 12 h in 80 DEG C of vacuum drying oven；Wherein, ZnO/ZnFe2O4Hollow nanometer bouquet, AgNO3、C6H4
(COOH)2, ethylene glycol mass ratio are as follows: 1~2: 0.4~1: 0.5~1；The oil bath temperature is 100~140 DEG C, when reaction
Between be 1~3 h；
Step 4: deposition surface Raman-active species
The active material that step 3 is synthesized is configured to the uniform solution of 10 mg/mL, and with model machine, 10 μ L are evenly spaced every time
Bottom is added dropwise to have already passed through on load fragment or the silicon wafer of PDMS modification added with magnet, is then put in 30~60 DEG C of constant temperature and humidity
It is deposited in case, forms coffee spot array to it, just obtained the dense form Raman spectrum base.
Dense form Raman spectrum base made from a kind of above method.
The dense form Raman spectrum base is with a thickness of 30~50 μm, and a diameter of 300~700 μm.
A kind of application of above-mentioned dense form Raman spectrum base, the substrate are applied to bacillus anthracis marker
Trace detection in environment and life, being capable of effective monitoring and analysis anthrax bar in the case where being not directly contacted with bacterium source
Bacterium.
The application of the substrate is specifically: 10 μ L pyrrole of various concentration is added dropwise in dense form Raman spectrum base
Diphosphoglyceric acid's solution (DPA) evaporates solvent under normal environment, is carried out using thermo Scientific DXR2 Raman spectrometer
Signal acquisition, 785 nm of optical maser wavelength, laser power are 0.24 mW, and acquisition time is 5 s；Collect Raman signal figure, root
The type and concentration of object are determined according to peak value and intensity size.
Compared with prior art, beneficial effect of the present invention includes the following:
The present invention, which sufficiently combines, inhibits coffee ring effect and a kind of fine and close coffee spot substrate of magnetic field control deposition self assembly, provides
The preparation method of the active Raman substrate simple and convenient, inexpensive, the period is short.Substrate surface Raman-active species use hydro-thermal
Method and pyrolysismethod are prepared for the ZnO-ZnFe with heterojunction structure2O4The hollow bouquet of@Ag composite Nano.Heterojunction structure improves
The stability of silver nano-grain ensure that the stability and reproducibility of prepared substrate.Provide a method it is simple and safe, when
Between it is short, fast and accurately detect environment in bacillus anthracis marker new opplication；ZnO-ZnFe2O4Carrier Raman enhancement effect
And the high surface area of substrate, inhibition coffee ring effect, the enriched multiple effect of magnetic field control also contribute to realizing to low concentration
The detection of object.Suitable for most determinand and enrichment method it is simple, inexpensively, quickly；Pass through bacillus anthracis marker
Its concentration of the variation indirect determination bacillus anthracis to be measured of concentration, easy to operate, detection time is short, detection limit is down to 10-8M has
Reproducibility is high, stability is good, example enrichment, can long-term preservation the advantages that.The present invention is controlled using inhibition coffee ring effect and magnetic field
The coffee spot substrate of self assembly densification processed, the enhancement factor for calculating the substrate is 5 × 106, using the substrate to bacillus anthracis mark
Will object (DPA) realizes highly sensitive detection, and the detection range of linearity is 1 × 10-8~1 × 10-4Mol/L, linearly dependent coefficient
Reach 0.97, while this method stability and favorable reproducibility are in other Raman detection methods.Therefore this method quick and precisely, operation
Simply, it can be used for the quick detection of DPA in environment and life.
Detailed description of the invention
Fig. 1 is preparation and its detection bacillus anthracis marker applicating flow chart of dense form Raman substrate of the present invention；
Fig. 2 is the intermediate ZnO-ZnFe of Raman substrate active material prepared by the present invention2O4With target product ZnO-ZnFe2O4@
Scanning electron microscope (SEM) photograph of the Ag in different amplification；
Fig. 3 is the intermediate ZnO-ZnFe of Raman substrate active material prepared by the present invention2O4EDS elemental analysis map (figure
3a) and target product ZnO-ZnFe2O4The EDS elemental analysis map (Fig. 3 b) of@Ag；
Fig. 4 is the intermediate ZnO-ZnFe of Raman substrate active material prepared by the present invention2O4With target product ZnO-ZnFe2O4@
The XRD spectrum of Ag；
Fig. 5 is the coffee spot base that Raman substrate active material of the present invention is formed under the control of modification polytetrafluoroethylene (PTFE) glass slide magnetic field
Bottom and the comparison diagram that unmodified polytetrafluoroethylene (PTFE) glass slide formation substrate is controlled without magnetic field；
Fig. 6 is sensitivity test and dependent linearity figure of the coffee spot substrate prepared by the present invention to bacillus anthracis marker DPA；
Fig. 7 is selective map of the coffee spot substrate prepared by the present invention to bacillus anthracis marker DPA difference analog.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following embodiment.Without departing from the spirit and scope of the invention, this neighborhood technique personnel it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection scope.Implement process of the invention,
Condition, reagent, experimental method etc. are in addition to what is specifically mentioned below the universal knowledege and common knowledge of this neighborhood,
There are no special restrictions to content by the present invention.
Embodiment 1
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application, comprising the following specific steps
Step 1: the glass slide of cleaning deposition Raman-active species
The glass slide having a size of 2 cm X, 2 cm will be cut into and first wash surface smut with detergent, then cleaned with clear water
Fall detergent, then removed surface impurity with the HF of 20 % ten minutes, is respectively cleaned by ultrasonic 20 min with acetone, alcohol, finally goes
Ionized water is cleaned by ultrasonic 30 min, and taking-up, which is put into 50 DEG C of baking ovens, to be dried for standby；
Step 2: modification polymethyl siloxane (PDMS) is in glass slide
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is put into vacuum oven 20 min that deaerate, so
Afterwards, processed high polymer is uniformly revolved and is applied to glass slide surface.It is placed in 100 DEG C of baking ovens and solidifies 30 min, take out
Being cooled to room temperature, to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 1.0636g Zn (NO3)2﹒ 6H2O and 0.3552g Fe (acac)3It is dissolved in 50 mL DMF
In the alcohol mixed solution of 30 mL.Then, by the terephthalic acid (TPA) (H of 80 mg2) and the PVP(K30 of 60 mg, Mw BDC
=40,000) it is added with stirring in above-mentioned solution in violent, then is placed in the stainless steel sealing container of teflon lined
It (100 mL) and is heated 18 hours at 180 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing
For several times.Product is 24 hours dry at 80 DEG C, and it is expressed as Zn/Fe-MOFs；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat rate be 2 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
In further reaction, 100 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 50 mL ethylene glycol round bottoms
In flask.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
40 mg AgNO of middle addition3, go forward side by side 3 h of single step reaction.After cooled to room temperature, by the way that product is collected by centrifugation and spends
Ion water washing dries 12 h three times, by product in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, takes the evenly spaced dropwise addition bottom 10 μ L respectively every time
Portion is had already passed through added with magnet in the glass slide of PDMS modification, is then put in 40 DEG C of climatic chamber to its formation
Coffee spot array has just obtained the substrate with surface-enhanced Raman effects；
Step 5: detection bacillus anthracis marker:
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 2
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application, comprising the following specific steps
Step 1: the silicon wafer of cleaning deposition Raman-active species
The silicon wafer having a size of 1.5cm X 1.5cm will be cut into and first wash surface smut with detergent, then washed and washed with clear water
Agent is washed, is then soaked in Piranha solution ten minutes and removes surface impurity, be respectively cleaned by ultrasonic 20 min with acetone, alcohol, finally
Deionized water is cleaned by ultrasonic 30 min, and taking-up, which is put into 60 DEG C of baking ovens, to be dried for standby；
Step 2: modification polymethyl siloxane (PDMS) is in silicon wafer
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is then placed in vacuum oven and deaerates 20
Then processed high polymer is uniformly revolved and is applied to silicon chip surface by min；It is placed in 120 DEG C of baking ovens and solidifies 20 min, take out
Being cooled to room temperature, to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 2.0 g Zn (NO3)2﹒ 6H2O and 0.6 g Fe (acac)3It is dissolved in 50 mL DMF and 50
In the alcohol mixed solution of mL.Then, by the terephthalic acid (TPA) (H of 100 mg2) and the PVP(K30 of 100 mg, BDC Mw=40,
000) the stainless steel sealing container that is then placed into teflon lined will be added in above-mentioned solution under violent stirring
(100 mL) and 18 h are heated at 180 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing
For several times.Product is dried into 24 h at 80 DEG C, and is expressed as Zn/Fe-MOFs.
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe-MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat rate be 2 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
In further reaction, 150 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 80 mL ethylene glycol round bottoms
In flask.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
100 mg AgNO of middle addition3, go forward side by side 3 h of single step reaction.After cooled to room temperature, by the way that product is collected by centrifugation and spends
Ion water washing dries 12 h three times, by product in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, takes the evenly spaced dropwise addition bottom 10 μ L respectively every time
Portion is had already passed through added with magnet on the silicon wafer of PDMS modification, is then put in 40 DEG C of climatic chamber and is formed coffee spot to it
Array has just obtained the substrate with surface-enhanced Raman effects；
Step 5: detection bacillus anthracis marker:
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 3
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application (such as Fig. 1), comprising the following specific steps
Step 1: the glass slide of cleaning deposition Raman-active species
The glass slide having a size of 2.5 cm X, 2.5 cm will be cut into and first wash surface smut with detergent, then use clear water
Detergent is washed, is then soaked in Piranha solution ten minutes and removes surface impurity, be respectively cleaned by ultrasonic 20 with acetone, alcohol
Min, last deionized water are cleaned by ultrasonic 30 min, and taking-up, which is put into 60 DEG C of baking ovens, to be dried for standby；
Step 2: modification polymethyl siloxane (PDMS) is in glass slide
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is then placed in vacuum oven and deaerates 20
Then processed high polymer is uniformly revolved and is applied to glass slide surface by min.It is placed in 120 DEG C of baking ovens and solidifies 20
Min, taking-up is cooled to room temperature, and to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 1.5 g Zn (NO3)2﹒ 6H2O and 0.5 g Fe (acac)3It is dissolved in 100 mL DMF and 80
In the acetone mixed solution of mL.Then, by the terephthalic acid (TPA) (H of 100 mg2) and the PVP(K30 of 80 mg, BDC Mw=40,
000) the stainless steel sealing container that is then placed into teflon lined will be added in above-mentioned solution under violent stirring
(100 mL) and 16 h are heated at 200 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing
For several times.Product is dried into 24 h at 80 DEG C, and is expressed as Zn/Fe-MOFs；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe-MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat rate be 2 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
In further reaction, 100 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 70 mL ethylene glycol circle
In the flask of bottom.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
70 mg AgNO are added in liquid3, go forward side by side 3 h of single step reaction.After cooled to room temperature, it is used in combination by the way that product is collected by centrifugation
Deionized water is washed three times, and product is dried 12 h in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, takes the evenly spaced dropwise addition bottom 10 μ L respectively every time
Portion is had already passed through added with magnet in the glass load fragment of PDMS modification, is then put in 40 DEG C of climatic chamber to its formation
Coffee spot array has just obtained the substrate with surface-enhanced Raman effects；
Step 5: detection bacillus anthracis marker
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 4
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application, comprising the following specific steps
Step 1: the silicon wafer of cleaning deposition Raman-active species
The silicon wafer having a size of 1 cm X, 1 cm will be cut into and first wash surface smut with detergent, washing washing with clear water
Then agent is soaked in Piranha solution ten minutes and removes surface impurity, then acetone, alcohol are respectively cleaned by ultrasonic 20 min, finally
Deionized water is cleaned by ultrasonic 30 min, and taking-up, which is put into 60 DEG C of baking ovens, to be dried for standby.
Step 2: modification polymethyl siloxane (PDMS) is in silicon wafer
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is then placed in vacuum oven and deaerates 20
Then processed high polymer is uniformly revolved and is applied to silicon chip surface by min.It is placed in 120 DEG C of baking ovens and solidifies 20 min, take out
Being cooled to room temperature, to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 2.0 g Zn (NO3)2﹒ 6H2O and 1.0 g Fe (acac)3It is dissolved in 100 mL DMF and 80
In the alcohol mixed solution of mL.Then, by the terephthalic acid (TPA) (H of 120 mg2) and the PVP(K30 of 100 mg, Mw BDC=
40,000) the stainless steel sealing container that is then placed into teflon lined will be added in above-mentioned solution under violent stirring
(100 mL) and 18 h are heated at 180 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing number
It is secondary.Product is dried into 24 h at 80 DEG C, and is expressed as Zn/Fe-MOFs；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe MOFs is calcined at 500 DEG C in tube furnace with air atmosphere, slow heat rate be 1 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
In further reaction, 100 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 50 mL ethylene glycol circle
In the flask of bottom.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
40 mg AgNO are added in liquid3, go forward side by side 3 h of single step reaction.After cooled to room temperature, it is used in combination by the way that product is collected by centrifugation
Deionized water is washed three times, and product is dried 12 h in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, takes the evenly spaced dropwise addition bottom 10 μ L respectively every time
Portion is had already passed through added with magnet on the silicon wafer of PDMS modification, is then put in 40 DEG C of climatic chamber and is formed coffee spot to it
Array has just obtained the substrate with surface-enhanced Raman effects；
Step 5: detection bacillus anthracis marker:
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 5
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application, comprising the following specific steps
Step 1: the silicon wafer of cleaning deposition Raman-active species
The silicon wafer having a size of 3 cm X, 3 cm will be cut into and first wash surface smut with detergent, then wash washing with clear water
Then agent is soaked in Piranha solution ten minutes and removes surface impurity, is respectively cleaned by ultrasonic 20 min with acetone, alcohol, finally goes
Ionized water is cleaned by ultrasonic 30 min, and taking-up, which is put into 60 DEG C of baking ovens, to be dried for standby；
Step 2: modification polymethyl siloxane (PDMS) is in silicon wafer
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is then placed in vacuum oven and deaerates 20
Then processed high polymer is uniformly revolved and is applied to slide surface by min.It is placed in 120 DEG C of baking ovens and solidifies 20 min, take
Being cooled to room temperature out, to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 1.8 g Zn (NO3)2﹒ 6H2O and 1.2 g Fe (acac)3It is dissolved in 80 mL DMF and 80
In the alcohol mixed solution of mL.Then, by the terephthalic acid (TPA) (H of 100 mg2) and the PVP(K30 of 80 mg, Mw BDC=
40,000) the stainless steel sealing container that is then placed into teflon lined will be added in above-mentioned solution under violent stirring
(100 mL) and 18 h are heated at 180 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing number
It is secondary.Product is dried into 24 h at 80 DEG C, and is expressed as Zn/Fe-MOFs；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe-MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat rate be 2 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
In further reaction, 200 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 70 mL ethylene glycol circle
In the flask of bottom.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
120 mg AgNO are added in liquid3, go forward side by side 3 h of single step reaction.After cooled to room temperature, it is used in combination by the way that product is collected by centrifugation
Deionized water is washed three times, and product is dried 12 h in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, sampling takes 10 intervals μ L uniform respectively every time manually
Dropwise addition bottom added with magnet have already passed through PDMS modification silicon wafer on, be then put in 40 DEG C of climatic chamber to its shape
At coffee spot array, the substrate with surface-enhanced Raman effects has just been obtained；
Step 5: detection bacillus anthracis marker
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 6
A kind of substrate of Surface enhanced Raman spectroscopy and its preparation method and application, comprising the following specific steps
Step 1: the glass slide or silicon wafer of cleaning deposition Raman-active species
The glass slide having a size of 3 cm X, 3 cm will be cut into and first wash surface smut with detergent, then cleaned with clear water
Fall detergent, be then soaked in Piranha solution ten minutes and remove surface impurity, be respectively cleaned by ultrasonic 20 min with acetone, alcohol,
Last deionized water is cleaned by ultrasonic 30 min, and taking-up, which is put into 60 DEG C of baking ovens, to be dried for standby；
Step 2: modification polymethyl siloxane (PDMS) is in glass slide
PDMS prepolymer is uniformly mixed with curing agent with mass ratio 10:1, is then placed in vacuum oven and deaerates 20
Then processed high polymer is uniformly revolved and is applied to slide surface by min.It is placed in 120 DEG C of baking ovens and solidifies 20 min, take
Being cooled to room temperature out, to be placed on clean stored box spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by 1.0636 g Zn (NO3)2﹒ 6H2O and 0.5 g Fe (acac)3Be dissolved in 50 mL DMF and
In the alcohol mixed solution of 50 mL.Then, by the terephthalic acid (TPA) (H of 100 mg2) and the PVP(K30 of 80 mg, Mw BDC=
40,000) the stainless steel sealing container that is then placed into teflon lined will be added in above-mentioned solution under violent stirring
(100 mL) and 18 h are heated at 180 DEG C.It is cooled to room temperature later, collects sediment and be centrifuged and use DMF and ethanol washing number
It is secondary.Product is dried into 24 h at 80 DEG C, and is expressed as Zn/Fe-MOFs；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat rate be 2 DEG C/
Min is cooled to room temperature after the completion of calcining to obtain classification spherical shape ZnO/ZnFe2O4Hollow nanospheres；
(3) ZnO-ZnFe is prepared2O4The hollow nanometer bouquet of@Ag
In further reaction, 100 mg ZnO/ZnFe has been synthesized into2O4Nanosphere is added to containing 80 mL ethylene glycol round bottoms
In flask.Then round-bottomed flask is placed in oil bath and is heated to 120 DEG C.After keeping 1 h of temperature at 120 DEG C, to suspension
50 mg AgNO of middle addition3, go forward side by side 5 h of single step reaction.After cooled to room temperature, by the way that product is collected by centrifugation and spends
Ion water washing dries 12 h three times, by product in 80 DEG C of vacuum drying oven；
Step 4: deposition surface Raman-active species
The active material of synthesis is configured to the uniform solution of 10 mg/mL, takes the evenly spaced dropwise addition bottom 10 μ L respectively every time
Portion is had already passed through added with magnet in the load fragment of PDMS modification, is then put in 40 DEG C of climatic chamber and is formed coffee to it
Spot array has just obtained the substrate with surface-enhanced Raman effects；
Step 5: detection bacillus anthracis marker:
10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration is added dropwise in the surface Raman substrate prepared, is evaporated under normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s.The substrate is applied to trace detection of the bacillus anthracis marker in environment and life,
It can effective monitoring and analysis bacillus anthracis in the case where being not directly contacted with bacterium source.
Embodiment 7
The preparation and its detection bacillus anthracis marker applicating flow chart (such as Fig. 1) of dense form Raman substrate of the present invention, will synthesize
ZnO/ZnFe2O4The nanoparticle activated substance of@Ag is configured to the uniform solution of 10 mg/mL, and with model machine, 10 intervals μ L are equal every time
Even dropwise addition bottom has already passed through on load fragment or the silicon wafer of PDMS modification added with magnet, is then put in 30~60 DEG C of constant temperature
It is deposited in constant humidity cabinet, forms coffee spot array to it, just obtained the dense form Raman spectrum base, it will
The dropwise addition of 10 μ L pyridinedicarboxylic acid solution (DPA) of various concentration gradient is evaporated under the coffee class substrate that will be prepared, normal environment
Solvent carries out signal acquisition, 785 nm of optical maser wavelength, laser power using thermo Scientific DXR2 Raman spectrometer
For 0.24 mW, acquisition time is 5 s, will obtain Raman signal figure progress intensity and peaky fuzzy number determines its type and concentration.
Prepared by ZnO/ZnFe to embodiment 12O4@Ag nano particle and intermediate product ZnO/ZnFe2O4Nano particle carries out
Scanning transmission electron microscope (such as Fig. 2 a-h), intermediate product ZnO/ZnFe2O4Nano particle EDS elemental analysis figure (such as Fig. 3 a) and ZnO/
ZnFe2O4@Ag nano particle EDS elemental analysis figure (such as Fig. 3 b), XRD characterization (such as Fig. 4) are from the material known to transmission electron microscope
A kind of tactical rule, the bouquet structure that outer surface is made of lamella, by elemental analysis the result shows that the bulk composition of the material is
(such as Fig. 3 b) that the elements such as Zn, Fe, O and Ag are constituted, intermediate product do not occur the peak (such as Fig. 3 a) of Ag element then.It will preparation
ZnO/ZnFe2O4@Ag carries out XRD characterization, and XRD diffraction shows ZnO/ZnFe2O4@Ag and intermediate product ZnO/ZnFe2O4Nanometer
Grain peak value complies with standard six side ZnO structure (JPCDS:36-1451) lattice parameters and cube ZnFe2O4(JPCDS:22-1012)
Lattice parameter.And ZnO/ZnFe2O4The peak that simple substance Ag occurs in@Ag is consistent with Ag(JPCDS:04-0783) standard card, card
Bright ZnO/ZnFe2O4@Ag nano particle successfully synthesizes, and occurs without other impurity peaks, demonstrates the purity of composite material.Benefit
There is no magnetic field controls for the base pattern (such as Fig. 5 a) and unused PDMS modification substrate formed with PDMS modification substrate combined magnetic field
System is formed by base pattern comparison (such as Fig. 5 b), and it is smaller and be in control formed pattern using PDMS modification substrate combined magnetic field
Existing densification regular circle shapes, the presented pattern that the strategy is not used is larger and be not have well-regulated pattern, and coffee ring effect is obvious
Structure is loosely.Coffee spot substrate shows high SERS sensitivity and detection limit down to 10 to DPA-8M(such as Fig. 6), and have good
Linear relationship, R2Reach 0.97.And the substrate can successfully distinguish (such as Fig. 7) analog of DPA.
The invention discloses substrate of a kind of Surface enhanced Raman spectroscopy and its preparation method and application, which includes glass
Glass glass slide, modify in polymethyl siloxane (PDMS) coating of glass slide, be covered on coating by hollow magnetic ZnO/
ZnFe2O4The coffee spot deposit with certain thickness densification of@Ag nano particle composition, to obtain with surface enhanced drawing
The active substrate of graceful effect；The substrate passes through preparation enhancing Raman active material, glass slide cleaning, polymethyl siloxane (PDMS)
Modification, the deposition of Raman active material and etc. acquisition, utilize magnetic field effect and inhibit coffee ring effect self assembly deposition side
Method prepares substrate, this method have it is convenient and simple, it is low in cost, it is easy to accomplish and sample treatment it is simple the advantages that.It should
SERS of the substrate for bacillus anthracis marker is detected, and detection sensitivity and stability with higher are being not directly contacted with bacterium
In the case where source can effective monitoring and analysis bacillus anthracis, in environment, there is very huge application prospect in the fields such as medical treatment.
In summary it is only presently preferred embodiments of the present invention, is not used to limit the scope of the invention.It is all according to the present invention
Equivalent changes and modifications made by content all should be protection category of the present invention.
Claims (5)
1. a kind of preparation method of dense form Raman spectrum base, which is characterized in that this method includes in detail below
Step:
Step 1: the glass slide or silicon wafer of cleaning deposition Raman-active species
Glass slide having a size of (1~3) cm X (1~3) cm or silicon wafer will be cut into and first wash surface dirt with detergent
Then dirt, then wash detergent with clear water impregnates ten minutes with reagent to remove its oxide on surface, then with acetone, alcohol
20~40 min of each ultrasonic cleaning, last deionized water are cleaned by ultrasonic 30~50 min, and taking-up, which is put into 50~70 DEG C of baking ovens, dries
It does spare；The reagent is the HF of 10~30 % of concentration, one or more of the NaOH of 5~20 % of concentration and Piranha solution
Mixing；Wherein, the Piranha solution is the mixed solution of the 98 % concentrated sulfuric acids and 30 % hydrogen peroxide with volume for 7:3；
Step 2: modification polymethyl siloxane is in glass slide or silicon wafer
Polymethyl siloxane prepolymer is uniformly mixed with curing agent with 10~12:1 of mass ratio, is then placed in vacuum oven
It deaerates after 20~40 min, it is uniformly spun on glass slide or silicon chip surface with equal glue machine, is placed in baking oven and solidifies, Gu
Changing temperature is 80~120 DEG C, and curing time is 20~40 min；Solidification end taking-up is cooled to room temperature and is placed on clean stored
Box is spare；
Step 3: synthesis Raman-active species ZnO/ZnFe2O4@Ag nano particle
(1) Zn/Fe-MOFs presoma is prepared
First under magnetic stirring by Zn (NO3)2﹒ 6H2O and Fe (acac)3It is dissolved in oil phase solvent and aqueous phase solvent mixed solution
In；Then, by terephthalic acid (TPA) (C6H4(COOH)2) and PVP(K30, Mw=40,000) it is violent be added with stirring it is described
In mixed solution, it is placed in the stainless steel sealing container of teflon lined, and is heated 18 hours at 180 DEG C；It is cold later
But it to room temperature, collects sediment and is centrifuged and uses DMF and ethanol washing for several times；Product is dried into 24 h at 80 DEG C, and is expressed as
Zn/Fe-MOFs；Wherein, Zn (NO3)2﹒ 6H2O、Fe(acac)3、C6H4(COOH)2, PVP molar ratio are as follows: 3.5~5: 1~2:
0.5~1: 2 X 10-6~4 X 10-6, the oil phase solvent be DMF, NMP or DMSO, the aqueous phase solvent be ethyl alcohol, acetone or
Tetrahydrofuran；Wherein, the volume ratio of oil phase solvent and aqueous phase solvent are as follows: 2~4: 2~1；Reaction temperature used is 150~200
DEG C, the reaction time is 15~24 h；
(2) ZnO-ZnFe is prepared2O4Hollow nanometer bouquet intermediate
Synthesized Zn/Fe-MOFs is calcined at 600 DEG C in tube furnace with air atmosphere, slow heat, rate be 2 DEG C/
Min, calcines 3~5 h, is cooled to room temperature after the completion of calcining, is classified spherical shape ZnO/ZnFe to obtain2O4Hollow nanometer bouquet；Tubular type
Furnace calcination temperature is 500~700 DEG C, and heating rate is 1~5 DEG C/min；
(3) Raman-active species ZnO/ZnFe is synthesized2O4@Ag nano particle
The ZnO/ZnFe that will have been synthesized2O4Hollow nanometer bouquet is added to containing in ethylene glycol round-bottomed flask；Then by round-bottomed flask
It is placed in oil bath and is heated to 120 DEG C；After keeping 1 h of temperature at 120 DEG C, AgNO is added into suspension3, and it is further anti-
Answer 3 h；After cooled to room temperature, by the way that product is collected by centrifugation and is washed with deionized three times, by product at 80 DEG C
Dry 12 h in vacuum drying oven；Wherein, ZnO/ZnFe2O4Hollow nanometer bouquet, AgNO3, ethylene glycol mass ratio are as follows: 1~2:
0.4~1: 0.5~1；The oil bath temperature is 100~140 DEG C, and the reaction time is 1~3 h；
Step 4: deposition surface Raman-active species
The active material that step 3 is synthesized is configured to the uniform solution of 10 mg/mL, and with model machine, 10 μ L are evenly spaced every time
Bottom is added dropwise to have already passed through on load fragment or the silicon wafer of PDMS modification added with magnet, is then put in 30~60 DEG C of constant temperature and humidity
It is deposited in case, forms coffee spot array to it, just obtained the dense form Raman spectrum base.
2. dense form Raman spectrum base made from a kind of claim 1 the method.
3. dense form Raman spectrum base according to claim 2, which is characterized in that the substrate thickness is
30~50 μm, a diameter of 300~700 μm.
4. a kind of application of dense form Raman spectrum base as claimed in claim 2, which is characterized in that the substrate is answered
It, can be effective in the case where being not directly contacted with bacterium source for trace detection of the bacillus anthracis marker in environment and life
Monitoring and analysis bacillus anthracis.
5. application according to claim 4, which is characterized in that be added dropwise in dense form Raman spectrum base different
10 μ L pyridinedicarboxylic acid solution (DPA) of concentration evaporates solvent under normal environment, is drawn using thermo Scientific DXR2
Graceful spectrometer carries out signal acquisition, 785 nm of optical maser wavelength, and laser power is 0.24 mW, and acquisition time is 5 s；It collects
Raman signal figure determines the type and concentration of object according to peak value and intensity size.
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