阅读说明：本技术 一种二硫化钼/银纳米免疫基底材料的制备方法及其可重复免疫检测应用 (The preparation method and its repeatable immune detection application of base material is immunized in a kind of molybdenum disulfide/silver nanoparticle ) 是由 牛志强 姜涛 庄文婷 陈颖 顾辰杰 姜勇 王福艳 于 2019-07-11 设计创作，主要内容包括：本发明公开了一种二硫化钼/银纳米免疫基底材料的制备方法及其可重复免疫检测应用,特点是包括以下步骤：1)二硫化钼纳米材料的制备；2)将二硫化钼纳米材料溶液旋涂在干净硅片上真空干燥后,采用磁控溅射的方法于硅片表面溅射一层Ag纳米颗粒得到二硫化钼/银纳米材料,3)将抗体连接到二硫化钼/银纳米材料上后得到二硫化钼/银纳米免疫基底材料；其免疫检测方法如下：将待测抗原滴加到二硫化钼/银纳米免疫基底材料上孵育后,滴加金纳米棒免疫探针溶液后进行光谱测量,经催化降解后二硫化钼/银纳米材料可实现对癌症标志物的可重复免疫检测,优点是检测限低且可重复循环利用。(The invention discloses base material is immunized in a kind of molybdenum disulfide/silver nanoparticle preparation methods and its repeatable immune detection application, and feature is the following steps are included: the 1) preparation of molybdenum disulfide nano material；2) molybdenum disulfide nano material solution is spin-coated on after being dried in vacuo on clean silicon wafer, sputter one layer of Ag nano particle in silicon chip surface using the method for magnetron sputtering and obtain molybdenum disulfide/silver nano material, 3) molybdenum disulfide/silver nanoparticle is obtained after antibody being connected on molybdenum disulfide/silver nano material, and base material is immunized；Its immunologic detection method is as follows: determined antigen being added drop-wise to molybdenum disulfide/silver nanoparticle and is immunized on base material after incubation, spectral measurement is carried out after gold nanorod immunoprobe solution is added dropwise, molybdenum disulfide/silver nano material can realize the repeatable immune detection to cancer markers after catalytic degradation, and advantage is that detection limit is low and repeatable recycle.)

1. the preparation method that base material is immunized in a kind of molybdenum disulfide/silver nanoparticle, it is characterised in that the following steps are included:

(1) preparation of molybdenum disulfide nano material

Sodium molybdate dihydrate, thioacetamide and Silicotungstic acid hydrate are pressed 0.3629-1.0887 grams: 0.33809- 1.01427 grams: 4.0294-12.0882 grams: 25-75 milliliters of ratio is add to deionized water, and stirring makes it in 15-25 minutes After mixing, be added dropwise sodium hydrate aqueous solution adjust solution ph be 7.62 after, above-mentioned reaction solution is transferred to water It is sealed in thermal response kettle, is placed at 200-240 DEG C and reacts 22-26 hours, after reaction kettle cooled to room temperature, be obtained by filtration Solid product is successively used sodium hydrate aqueous solution, dehydrated alcohol and deionized water washing, washes repeatedly 1- altogether by solid product 3 times, then solid product is placed in be dried in vacuo 10-14 hours at 45-55 DEG C and obtains molybdenum disulfide nano material；

(2) molybdenum disulfide/silver nano material preparation

The molybdenum disulfide nano material powder that step (1) obtains, which is dissolved in ultrasound in deionized water, is uniformly mixed it, The molybdenum disulfide nano material solution that concentration is 30 mg/mls is obtained, molybdenum disulfide nano material solution is spin-coated on completely It on silicon wafer, places it at 45-55 DEG C after being dried in vacuo 10-14 hours, is sputtered using the method for magnetron sputtering in silicon chip surface One layer of silver nano-grain to get arrive molybdenum disulfide/silver nano material；

(3) preparation of base material is immunized in molybdenum disulfide/silver nanoparticle

By 0.2 milliliter containing 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide After PBS mixed solution is added drop-wise on molybdenum disulfide/silver nano material that 1 milligram of step (2) obtains, it is placed in 37 DEG C and is incubated for 1 hour, It uses PBS solution repeated flushing 3 times again；Then the PBS buffer solution of the 20-60 microlitres of antibody containing cancer markers is added dropwise in 2-6 DEG C Lower incubation 10-14 hours, then after successively cleaning the extra unreacted antibody of removal with TBS solution, PBS solution and deionized water, The 10-60 microlitres of PBS buffer solution containing bovine serum albumin(BSA) is added dropwise again to react at room temperature 1 hour, cleaning removal is not extra anti- Base material is immunized to get to molybdenum disulfide/silver nanoparticle after the bovine serum albumin(BSA) answered, is placed at 4 DEG C and stores for use.

2. the preparation method of base material is immunized in a kind of molybdenum disulfide/silver nanoparticle according to claim 1, feature exists In: the concentration of sodium hydrate aqueous solution as described in step (1) is 1 mM every milliliter.

3. the preparation method of base material is immunized in a kind of molybdenum disulfide/silver nanoparticle according to claim 1, feature exists The magnetically controlled sputter method used in: step (2), sputtering condition are 0.3 pa of vacuum degree, 50 watts of power, sputtering time 60-140 Second.

4. the preparation method of base material is immunized in a kind of molybdenum disulfide/silver nanoparticle according to claim 1, feature exists In: contain 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimidyl acyl Asia described in step (3) The concentration of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is 2 milligrams every milliliter in the PBS mixed solution of amine, The concentration of n-hydroxysuccinimide is 1 milligram every milliliter；Cancer in the PBS buffer solution of the antibody containing cancer markers Marker antibody concentration is 2 mg/mls, bovine serum albumin(BSA) in the PBS buffer solution containing bovine serum albumin(BSA) Mass percent is 3%.

5. the cancer markers of base material are immunized based on molybdenum disulfide/silver nanoparticle of any of claims 1-4 Repeatable immunologic detection method, it is characterised in that the following steps are included:

(1) immune detection of cancer markers

20 microlitres of buffer solutions containing cancer markers antigen to be measured are added drop-wise to two sulphur made from any one of claim 1-4 Change molybdenum/silver nanoparticle to be immunized on base material, be subsequently placed at 37 DEG C and be incubated for 2 hours, cleaning removal is extra unreacted to be measured anti- After original, it is molten that 15 microlitres of gold nanorod immunoprobes of dropwise addition in substrate are immunized to the molybdenum disulfide/silver nanoparticle for being adsorbed with determined antigen Liquid is incubated for 2 hours at 37 DEG C, and cleaning removes extra unreacted gold nanorod immunoprobe, using Raman spectrometer to upper It states the gold nanorod immunoprobe obtained after immune response and the compound progress spectrum survey of substrate is immunized in molybdenum disulfide/silver nanoparticle Amount, according to the linear relationship between cancer markers antigen concentration and Raman signatures peak intensity, is calculated cancer mark to be measured The concentration of object antigen；

(2) molybdenum disulfide/silver nano material recovery method

After spectral detection, using ultraviolet lamp irradiating sample 2 hours, photocatalysis removed molybdenum disulfide/silver nanoparticle and substrate is immunized On determined antigen and antibody, with phosphate buffer solution rinse molybdenum disulfide/silver nanoparticle be immunized substrate, wash away remaining Jenner Rice stick immunological probe, the molybdenum disulfide/silver nano material cleaned up is formed in conjunction with cancer markers antibody again new Substrate is immunized in molybdenum disulfide/silver nanoparticle, and the repeatable immune detection to cancer markers can be realized in repetitive operation step (1).

6. the cancer markers according to claim 5 that base material is immunized based on molybdenum disulfide/silver nanoparticle is repeatable Immunologic detection method, it is characterised in that the preparation method of the gold nanorod immunoprobe is specific as follows: dense by 5-20 milliliters Degree is 0.0005 mM every for 0.1 mM every milliliter of cetyl trimethylammonium bromide aqueous solution and 5-20 milliliters of concentration After the aqueous solution of chloraurate of milliliter is mixed, the boron hydrogen that 0.3-1.2 milliliters of concentration are 0.01 mM every milliliter is rapidly joined Change sodium water solution, lasting stirring after ten minutes, stands 2 hours formation gold nano seed aqueous solutions at room temperature；By 47.5-190 Milliliter concentration be 0.1 mM every milliliter cetyl trimethylammonium bromide aqueous solution, 0.5-2 milliliters of concentration be 0.01 mmoles Aqueous solution of chloraurate, the 0.275- of the silver nitrate aqueous solution of every milliliter of that, 2.5-10 milliliters of concentration for 0.01 mM every milliliter The aqueous ascorbic acid and 0.08-0.32 milliliters of above-mentioned gold nano seeds that 1.1 milliliters of concentration are 0.1 mM every milliliter are water-soluble Liquid after mixing, stands reaction and obtains gold nanorods aqueous solution in 15 hours, and gold nanorods are dissolved in PBS again by being centrifugated In buffer solution；The buffer solution of 1-3 milliliters of gold nanorods is taken, it is 2 mg/mls that 20-60 microlitres of concentration is added thereto The PBS buffer solution of antibody is incubated for 1.5 hours at 4 DEG C, after centrifuge washing removes extra unreacted antibody, thereto plus Enter the buffer solution for the bovine serum albumin(BSA) that 5-20 microlitres of mass percent is 3%, is incubated for 1 hour at normal temperature, to close Jenner For rice stick not by the site of antibody attachment, centrifugation obtains the immune spy of gold nanorods after removing extra unreacted bovine serum albumin(BSA) Needle is placed at 4 DEG C and stores for use.

7. the cancer markers according to claim 6 that base material is immunized based on molybdenum disulfide/silver nanoparticle is repeatable Immunologic detection method, it is characterised in that: the centrifugal speed is 8000-16000 revs/min, and centrifugation time is 5-20 minutes.

8. the cancer markers according to claim 6 that base material is immunized based on molybdenum disulfide/silver nanoparticle is repeatable Immunologic detection method, it is characterised in that: the cancer markers antigen includes prostate-specific antigen PSA, alpha-fetoprotein Antigen A FP, ferritin antigen, sugar antigen CA199 and Carcinoembryonic Antigen CEA.

Technical field

The present invention relates to material engineering and field of nanometer technology, more particularly, to a kind of molybdenum disulfide/silver (MoS₂/ Ag) it receives The preparation method and its repeatable immune detection application of the immune base material of rice.

Background technique

Due to having the characteristics that incubation period is long, discovery is late and easily lethal, cancer has seriously endangered health and the society of the mankind The sustainable development of meeting.Early discovery early treatment has become the key of cancer diagnosis treatment, and therefore, science and technology and medical workers are Focus of attention is placed in the development and optimization of cancer early screening technology.Surface enhanced based on noble metal nanometer material is drawn Graceful scattering technology is had been attached great importance due to the sensitivity with superelevation, stable reproducibility and shirtsleeve operation method. A kind of novel immune analytical technology based on Surface enhanced Raman scattering technology is quietly risen in recent years.And semiconductor material due to Ability with Chemical enhancement can also assist the Electromagnetic enhancement of noble metal nanometer material to further enhance Raman signal.Together When, the chemical bond abundant that semiconductor material surface has is conducive to the absorption of trace testing molecule, can also reduce drawing indirectly Graceful detectable limit.Especially many semiconductor materials have photocatalytic activity, can by ultraviolet lighting generate light induced electron and Organic molecule is decomposed in hole pair, has the potentiality for realizing repeatable immune detection.In a series of semiconductor material, molybdenum disulfide (MoS₂) be widely adopted due to the advantages such as, pattern simple with preparation method are various and photocatalytic activity is stronger.Therefore, will MoS₂It is introduced into noble metal Raman substrate, develops a kind of novel repeatable immune inspection based on Surface enhanced Raman scattering technology Survey technology by be greatly promoted cancer markers early screening and diagnostic techniques it is abundant and perfect.But due to cancer mark Will object is macromolecular, is not easy to be catalytically decomposed, and uses the silver nano-grain stock size of chemical method synthesis more uneven, with MoS₂In conjunction with more open, it is unfavorable for improving MoS₂Catalytic activity, realize the degradation of macromolecular.Therefore, it is necessary to further open Other synthetic technologys are sent out, by noble silver nano particle and MoS₂Being implemented in combination with can be weighed based on Surface enhanced Raman scattering technology Multiple immune detection.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of detection limit the low and repeatable molybdenum disulfide recycled/ The preparation method and its repeatable immune detection application of base material is immunized in silver nanoparticle.

The technical scheme of the invention to solve the technical problem is: substrate is immunized in a kind of molybdenum disulfide/silver nanoparticle The preparation method of material, comprising the following steps:

(1) preparation of molybdenum disulfide nano material

Sodium molybdate dihydrate, thioacetamide and Silicotungstic acid hydrate are pressed 0.3629-1.0887 grams: 0.33809- 1.01427 grams: 4.0294-12.0882 grams: 25-75 milliliters of ratio is add to deionized water, and stirring makes it in 15-25 minutes After mixing, be added dropwise sodium hydrate aqueous solution adjust solution ph be 7.62 after, above-mentioned reaction solution is transferred to water It is sealed in thermal response kettle, is placed at 200-240 DEG C and reacts 22-26 hours, after reaction kettle cooled to room temperature, be obtained by filtration Solid product is successively used sodium hydrate aqueous solution, dehydrated alcohol and deionized water washing, washes repeatedly 1- altogether by solid product 3 times, then solid product is placed in be dried in vacuo 10-14 hours at 45-55 DEG C and obtains molybdenum disulfide nano material；

(2) molybdenum disulfide/silver nano material preparation

The molybdenum disulfide nano material powder that step (1) obtains, which is dissolved in ultrasound in deionized water, is uniformly mixed it, The molybdenum disulfide nano material solution that concentration is 30 mg/mls is obtained, molybdenum disulfide nano material solution is spin-coated on completely It on silicon wafer, places it at 45-55 DEG C after being dried in vacuo 10-14 hours, is sputtered using the method for magnetron sputtering in silicon chip surface One layer of silver nano-grain to get arrive molybdenum disulfide/silver nano material；

(3) preparation of base material is immunized in molybdenum disulfide/silver nanoparticle

By 0.2 milliliter containing 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide After PBS mixed solution is added drop-wise on molybdenum disulfide/silver nano material that 1 milligram of step (2) obtains, it is placed in 37 DEG C and is incubated for 1 hour, It uses PBS solution repeated flushing 3 times again；Then the PBS buffer solution of the 20-60 microlitres of antibody containing cancer markers is added dropwise in 2-6 DEG C Lower incubation 10-14 hours, then after successively cleaning the extra unreacted antibody of removal with TBS solution, PBS solution and deionized water, The 10-60 microlitres of PBS buffer solution containing bovine serum albumin(BSA) is added dropwise again to react at room temperature 1 hour, cleaning removal is not extra anti- Base material is immunized to get to molybdenum disulfide/silver nanoparticle after the bovine serum albumin(BSA) answered, is placed at 4 DEG C and stores for use.

The concentration of sodium hydrate aqueous solution as described in step (1) is 1 mM every milliliter.

The magnetically controlled sputter method used in step (2), sputtering condition are 0.3 pa of vacuum degree, 50 watts of power, sputtering time 60-140 seconds.

Contain 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxyl amber described in step (3) The concentration of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is 2 milligrams every in the imido PBS mixed solution of amber Milliliter, the concentration of n-hydroxysuccinimide are 1 milligram every milliliter；The PBS buffer solution of the antibody containing cancer markers Middle cancer markers antibody concentration is 2 mg/mls, and ox blood is pure in the PBS buffer solution containing bovine serum albumin(BSA) The mass percent of albumen is 3%.

The repeatable immunologic detection method of the cancer markers of base material is immunized in above-mentioned molybdenum disulfide/silver nanoparticle, special Sign be the following steps are included:

(1) immune detection of cancer markers

20 microlitres of buffer solutions containing cancer markers antigen to be measured are added drop-wise to two sulphur made from any one of claim 1-4 Change molybdenum/silver nanoparticle to be immunized on base material, be subsequently placed at 37 DEG C and be incubated for 2 hours, cleaning removal is extra unreacted to be measured anti- After original, it is molten that 15 microlitres of gold nanorod immunoprobes of dropwise addition in substrate are immunized to the molybdenum disulfide/silver nanoparticle for being adsorbed with determined antigen Liquid is incubated for 2 hours at 37 DEG C, and cleaning removes extra unreacted gold nanorod immunoprobe, using Raman spectrometer to upper It states the gold nanorod immunoprobe obtained after immune response and the compound progress spectrum survey of substrate is immunized in molybdenum disulfide/silver nanoparticle Amount, according to the linear relationship between cancer markers antigen concentration and Raman signatures peak intensity, is calculated cancer mark to be measured The concentration of object antigen；

(2) molybdenum disulfide/silver nano material recovery method

After spectral detection, using ultraviolet lamp irradiating sample 2 hours, photocatalysis removed molybdenum disulfide/silver nanoparticle and substrate is immunized On determined antigen and antibody, with phosphate buffer solution rinse molybdenum disulfide/silver nanoparticle be immunized substrate, wash away remaining Jenner Rice stick immunological probe, the molybdenum disulfide/silver nano material cleaned up is formed in conjunction with cancer markers antibody again new Substrate is immunized in molybdenum disulfide/silver nanoparticle, and the repeatable immune detection to cancer markers can be realized in repetitive operation step (1).

The preparation method of the gold nanorod immunoprobe is specific as follows: being 0.1 mM every by 5-20 milliliters of concentration The gold chloride water that the cetyl trimethylammonium bromide aqueous solution of milliliter is 0.0005 mM every milliliter with 5-20 milliliters of concentration After solution is mixed, the sodium borohydride aqueous solution that 0.3-1.2 milliliters of concentration are 0.01 mM every milliliter is rapidly joined, is continued Stirring after ten minutes, stands 2 hours formation gold nano seed aqueous solutions at room temperature；It is 0.1 milli by 47.5-190 milliliters of concentration The nitric acid that mole every milliliter of cetyl trimethylammonium bromide aqueous solution, 0.5-2 milliliters of concentration are 0.01 mM every milliliter Aqueous solution of chloraurate that silver-colored aqueous solution, 2.5-10 milliliter concentration are 0.01 mM every milliliter, 0.275-1.1 milliliters of concentration are 0.1 mM every milliliter of aqueous ascorbic acid and 0.08-0.32 milliliter above-mentioned gold nano seed aqueous solution after mixing, It stands reaction and obtains gold nanorods aqueous solution in 15 hours, gold nanorods are dissolved in again in PBS buffer solution by being centrifugated；It takes The PBS buffering for the antibody that 20-60 microlitres of concentration is 2 mg/mls is added in the buffer solution of 1-3 milliliters of gold nanorods thereto Solution is incubated for 1.5 hours at 4 DEG C, and after centrifuge washing removes extra unreacted antibody, 5-20 microlitres of quality is added thereto The buffer solution for the bovine serum albumin(BSA) that percentage is 3% is incubated for 1 hour at normal temperature, attached not by antibody to close gold nanorods Site, centrifugation obtains gold nanorod immunoprobe after removing extra unreacted bovine serum albumin(BSA), is placed at 4 DEG C Storage is stand-by.

The centrifugal speed is 8000-16000 revs/min, and centrifugation time is 5-20 minutes.

The cancer markers antigen includes that prostate-specific antigen PSA, alpha-fetoprotein antigen A FP, ferritin are anti- Former, sugar antigen CA199 and Carcinoembryonic Antigen CEA.

Compared with the prior art, the advantages of the present invention are as follows: the invention discloses a kind of molybdenum disulfide/silver nanoparticles, and base is immunized The preparation method of bottom material and its repeatable immune detection application.This repeatable immunoassay technology will greatly reduce immune The cost of detection is conducive to it and is applied among the clinical detection of cancer.

In the present invention, molybdenum disulfide nano material has coarse surface texture, and silver nano-grain surface can be promoted electric The excitation in magnetic field obtains higher Raman signal enhancing efficiency.Meanwhile molybdenum disulfide nano material has biggish specific surface Product, there is higher photocatalytic activity.Its photocatalytic mechanism is under ultraviolet lighting, since the energy of photon is prohibited greater than molybdenum disulfide Bandwidth, the electronics (e in valence band^-) absorption photon energy is excited on conduction band, while hole (h is left in valence band⁺). When molybdenum disulfide is there are when surface defect or suitable trapping agent, the compound of electrons and holes is inhibited, will be in two sulphur Change molybdenum surface and oxidation-reduction reaction occurs.Valence band hole is good oxidant, can be with the H of molybdenum disulfide adsorption₂O The OH dissolved in molecule or reaction solution^-In conjunction with the hydroxyl radical free radical (OH) for forming oxidisability wave very living.And conduction band electron is good Good reducing agent, by with O that is molybdenum disulfide adsorption or being dissolved in reaction solution₂A series of intermediate reactions are carried out, most The hydroxyl radical free radical (OH) and Superoxide anion free radical (O of oxidisability wave very living can also be formed eventually₂ ^-).Hydroxyl radical free radical ( ) and Superoxide anion free radical (O OH₂ ^-) can be various organic matters (including this proteoglycan compound of Carcinoembryonic Antigen CEA) oxygen It is melted into CO₂、H₂The inorganic molecules such as O, and because their oxidability is strong, it can be ensured that oxidation reaction does not stay in generally Intermediate steps do not generate intermediate product.Meanwhile molybdenum disulfide surface covers a large amount of Ag nano particles by magnetron sputtering, when When having ambient light photograph, surface electronic can be excited to form local surface plasmon resonance, electronics a part of these excitations It can be reached by charge transfer process among the molybdenum disulfide conduction band near Ag nano particle, the electrons increased among conduction band Molybdenum disulfide is remarkably promoted to the catalytic degradation ability of Carcinoembryonic Antigen CEA.After catalytic degradation, by suitably cleaning, curing Molybdenum/silver nano material can also be recycled, and be detected in conjunction with new determined antigen again, realize a kind of circulation immunity inspection It surveys.Meanwhile the local enhancing electromagnetic field of Ag nano particle can significantly increase the Raman signal of Raman labels molecule, be conducive to reality The Surface enhanced Raman scattering base immune detection of the highly sensitive high specific of existing Carcinoembryonic Antigen CEA, in addition, molybdenum disulfide is coarse Surface be also beneficial to the absorption of testing molecule, realize the enhancing of Raman signal and the photocatalytic degradation of molecule.Molybdenum disulfide is received The silver nano-grain of rice material surface is coated using magnetron sputtering method, and method is simple, will not introduce other pollutants.Finally, adopting Use the anisotropy gold nanorods with cutting-edge structure as immunological probe, the surface charge assembled at tip is formed highly dense Raman signal is further amplified in degree local electromagnetism field energy, obtains higher sensitivity of immune detection.Therefore, using pair of the invention The repeatable immunologic detection method of cancer markers can obtain extremely low detectable limit by the detection of nearly 9 circulation immunities, right The detection limit of Carcinoembryonic Antigen CEA reaches 100 winged grams every milliliter.

Detailed description of the invention

Fig. 1 is the electron scanning micrograph of the molybdenum disulfide nano material prepared in the embodiment of the present invention 1；

Fig. 2 is the molybdenum disulfide/silver nanoparticle electron scanning micrograph prepared in the embodiment of the present invention 1；

Fig. 3 is to coat Ag particle preparation in molybdenum disulfide nano material surface prepared by embodiment 1 using PVP chemical reduction method Molybdenum disulfide/silver nano material electron scanning micrograph；

Fig. 4 is the electron scanning micrograph of the gold nanorod immunoprobe material prepared in the embodiment of the present invention 1；

Fig. 5 is that the repeatable immune base material of molybdenum disulfide/silver nanoparticle prepared in the embodiment of the present invention and gold nanorods are immune Probe material is by carrying out Raman detection to substrate after being immunoreacted with determined antigen (concentration is 0.2 milligram every milliliter) The obtained Raman spectrogram of Raman detection is carried out to substrate after obtained Raman spectrogram and ultraviolet lighting catalysis；

Fig. 6 is to coat Ag particle preparation in molybdenum disulfide nano material surface prepared by embodiment 1 using PVP chemical reduction method Molybdenum disulfide/silver nano material and gold nanorod immunoprobe material pass through and determined antigen (concentration is 0.2 milligram every milliliter) After being immunoreacted to substrate carry out after the obtained Raman spectrogram of Raman detection and ultraviolet lighting catalysis to substrate into The obtained Raman spectrogram of row Raman detection；

Fig. 7 is that the repeatable immune base material of molybdenum disulfide/silver nanoparticle prepared in the embodiment of the present invention 1 and gold nanorods are immune Probe material with the determined antigen of various concentration (concentration is 10 milligrams every milliliter to 100 winged grams every milliliter) by successively being exempted from The Raman spectrogram that Raman detection obtains is carried out to substrate after epidemic disease reaction；

Fig. 8 is that the repeatable immune base material of molybdenum disulfide/silver nanoparticle prepared in the embodiment of the present invention 1 and gold nanorods are immune Probe material carries out the Raman detection result during circulating immune reaction；

Fig. 9 is that the repeatable immune base material of molybdenum disulfide/silver nanoparticle prepared in the embodiment of the present invention 2 and gold nanorods are immune Probe material carries out the Raman detection result during circulating immune reaction；

Figure 10 is that the repeatable immune base material of molybdenum disulfide/silver nanoparticle prepared in the embodiment of the present invention 3 and gold nanorods are exempted from Epidemic disease probe material carries out the Raman detection result during circulating immune reaction.

Specific embodiment

The present invention will be described in further detail below with reference to the embodiments of the drawings.

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.Embodiment Used in Raman spectrum detector BWS415 be purchased from U.S. Bi Da Imtech (B&W Tek Inc.).It is adopted in following embodiment Antigen is Carcinoembryonic Antigen CEA and antibody is cancer embryo antibody, but is not limited only to Carcinoembryonic Antigen CEA, can also be special for prostate Specific Antigen PSA, alpha-fetoprotein antigen A FP, ferritin antigen and sugar antigen CA199 etc..