CN103147133A - Three-dimensional carrier of microarray biochip and preparation method thereof - Google Patents
Three-dimensional carrier of microarray biochip and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional carrier of a microarray biochip and a preparation method thereof. The three-dimensional carrier of a microarray biochip is prepared by growing a zinc oxide nanorod on the surface of a substrate material and growing a polymer brush on the surface of the zinc oxide nanorod. The preparation method comprises the following steps of: activating the surface of the substrate material, and growing a zinc oxide nanorod on the surface of the substrate material; performing surface modification on the grown zinc oxide nanorod; connecting the modified surface of the zinc oxide nanorod with an initiator; and finally, growing a polymer brush to obtain a three-dimensional carrier of a microarray biochip. The preparation method is simple, does not need special equipment, has low production cost and good repeatability, and can be used for realizing large-scale production; the prepared three-dimensional carrier has low price and high fixing density for probe molecule, can be used for effectively inhibiting non-specific protein adsorption and improving the sensitivity and the specificity, and can be widely applied to the fields of biology, basic medicine, disease diagnosis, drug screening, food safety, environmental monitoring and the like.
Description
Technical field
The invention belongs to detection field, relate to the three-dimensional carrier of micro-array biochip, also relate to the preparation method of this three-dimensional carrier.
Background technology
Micro-array biochip be with different bioprobe molecules such as DNA, antigen, antibody, aptamers etc. in order, high-density, be fixed on certain carrier addressable, cooperation is with the fluorescence reading system, realize a kind of technology of extensive, high throughput testing biomolecules and research bio-molecular interaction, at early screening, diagnosis and the treatment of disease and drug development, Basic Life scientific research important in inhibiting, obtained in recent years academia and industry member and studied widely interest.At present, the solid support material that micro-array biochip adopts is mainly surface-functionalized slide glass, the subject matter that this class solid support material exists is to be subject to the limited surface-area in slide glass one dimension surface, its probe molecule constant density is low, cause the sensitivity of micro-array biochip not high, detectability does not reach application request sometimes.for this problem, some macro-organism medical company have been developed the several high performance carrier, ONCYTE chip as GRACE BIO-LABS company, the PATH chip of GENTEL BIOSCIENCES company, the FAST chip of WHATMAN company, the SUPERPROTEIN chip of ARRAYIT company, the HYDROGEL chip of PERKIN-ELMER company, the MAXISORP chip of NALGE NUNC company, the hydrogel carrier of XanTec analytics etc., the common ground of these solid support materials is to have the three-dimensional carrier of surface micro-structure by employing, to improve the constant density of probe molecule, suppress simultaneously biomolecules in the non-specific adsorption on surface, to obtaining high detection sensitivity.But all there is different defectives in these commercial chips, for example need that complicated surface active, price are high, poor reproducibility, background signal be high, is difficult to satisfy the needs of scientific research and practical application.
Summary of the invention
In view of this, one of purpose of the present invention is to provide a kind of three-dimensional carrier of micro-array biochip, have the effect that price is low, the constant density of probe molecule is high, effectively suppress nonspecific proteins absorption, can satisfy in scientific research and practical application sensitivity and specific requirement; Two of purpose of the present invention is to provide the preparation method of micro-array biochip three-dimensional carrier, and the preparation method is simple.
For achieving the above object, the invention provides following technical scheme:
1. micro-array biochip three-dimensional carrier, described micro-array biochip three-dimensional carrier is at the substrate material surface growing zinc oxide nanorod, then gets at zinc oxide nano rod surface growth polymer brush.
Base material of the present invention can be sheet glass, plastic sheet, nylon membrane, silicon chip etc., and preferred, described base material is slide glass.
In the present invention, as long as in the zinc oxide nano rod surface growth, polymer brush is arranged, described polymer brush is preferably poly-(oligomeric ethylene glycol methacrylic ester-glycidyl methacrylate).
In the present invention, polymer brush can use the method growths such as self-organization, spin coating, and is preferred, and described polymer brush adopts surperficial Atom Transfer Radical Polymerization technology growth.
2. the preparation method of described micro-array biochip three-dimensional carrier, comprise the steps:
A. the surface with base material activates, then at the substrate material surface growing zinc oxide nanorod;
B. the zinc oxide nano rod with growth carries out finishing;
C. the zinc oxide nano rod surface after modification is connected into initiator;
D. be connected into the zinc oxide nano rod surface growth polymer brush of initiator, getting the three-dimensional carrier of micro-array biochip.
Preferably, in described step a, described activation is to be that 1-10mM potassium permanganate soaked 15-30 minute with base material concentration.
Preferably, in described step a, described growing zinc oxide nanorod is that the base material of activation is put into the mixing solutions that contains thanomin, ammoniacal liquor and zinc nitrate, growth is 30-60 minute in 65-95 ℃ of water-bath, in described mixing solutions, the final concentration of zinc nitrate is 10-100mM, the volume fraction of thanomin is 1-10%, and the volume fraction of ammoniacal liquor is 1-10%.
Preferably, described step b is that the base material after step a is processed is immersed in the ethanolic soln that contains the 3-glycidoxypropyl trimethoxysilane and soaked 1-3 hour, then with after alcohol flushing, and at 110 ℃ of temperature vacuum annealing 1-3 hour; In the ethanolic soln of the described 3-of containing glycidoxypropyl trimethoxysilane, the volumetric concentration of 3-glycidoxypropyl trimethoxysilane is 1%-5%.
Preferably, described step c is that the base material after step b is processed was put into the tetrahydrofuran solution that contains triethylamine and α-bromine isobutyl acylbromide or dichloromethane solution 2 hours, after taking out with tetrahydrofuran (THF) or dichloromethane rinse; In described tetrahydrofuran solution, the volume fraction of triethylamine is 0.2-0.4%, and the volume fraction of α-bromine isobutyl acylbromide is 0.4-0.6%.
Preferred, described steps d will be for being connected into the surperficial Atom Transfer Radical Polymerization technology growth polymer brush of zinc oxide nano rod surface employing of initiator.concrete steps contain 10-30%(v/v for first preparation) oligomeric ethylene glycol methacrylic ester (molecular-weight average 360) and the methanol/water solution of glycidyl methacrylate 0.4-1%(v/v), wherein the volume ratio of the methyl alcohol of methanol/water solution and water is 1:1, then blast nitrogen 15-30 minute in solution, add again 2, 2'-dipyridyl and cuprous bromide, to 2, the final concentration of 2'-dipyridyl is 3mg/mL, the final concentration of cuprous bromide is 1.7mg/mL's, after ultrasonic dissolution, slide glass after step c is processed immerses rapidly, sealing solution and the inert atmosphere case of inserting lucifuge are preserved and to be got final product in 6-12 hour.Wherein pass into nitrogen and can replace with that to add the concentration that is equivalent to liquor capacity 1/50 be the aqueous ascorbic acid of 120 mg/mL.
Beneficial effect of the present invention is: the invention discloses micro-array biochip three-dimensional carrier and corresponding preparation method, adopt wet chemical method and surperficial Atom Transfer Radical Polymerization technology in preparation, form the composite structure of zinc oxide nano rod and polymer brush at substrate material surface; The nano structure of zinc oxide that forms has huge specific surface area, can effectively improve the surface density of fixing biological probe molecule, and simultaneous oxidation zinc nanometer rod has the unique physical character of amplifying fluorescent signal, has greatly improved the signal to noise ratio of fluorometric analysis; And polymer brush is as decorative layer, can suppress effectively in solution on the one hand that in testing process, biomolecules in the non-specific adsorption on surface, has guaranteed the highly selective detection; On the other hand owing to containing micro-epoxide group (the GMA monomer carries) in polymer brush, under drying conditions can with the amino generation covalent cross-linking of bioprobe molecule, thereby the high-density of realization, high reactivity probe are fixed, so detection sensitivity is high, and lowest detectable limit reaches 100pg/mL; The three-dimensional carrier of the micro-array biochip that obtains can be applied to play a significant role in fundamental research and practical application.
Description of drawings
In order to make purpose of the present invention, technical scheme and beneficial effect clearer, the invention provides following accompanying drawing and describe:
Fig. 1 is micro-array biochip three-dimensional carrier preparation method and polymer brush schematic arrangement.
Fig. 2 is the electron scanning micrograph of zinc oxide nano rod.
Fig. 3 is the electron scanning micrograph of micro-array biochip three-dimensional carrier.
Fig. 4 is the micro-array biochip three-dimensional carrier transmission electron microscope photo of zinc oxide nano rod-polymer brush composite structure.
Fig. 5 is the infared spectrum (a: be zinc oxide nano rod infared spectrum figure of zinc oxide nano rod and zinc oxide nano rod-polymer brush composite structure; B: the infared spectrum of zinc oxide nano rod-polymer brush composite structure).
Fig. 6 is that (a is epoxy activation slide glass for fluorescence photo, fluorescence intensity and little spot diameter of the micro-array chip of 0.8mg/mL fluorescin (the anti-goat IgG of CY3 mark) on different carriers; B is that polymer brush is modified slide glass; C is that epoxy active oxidation zinc bar is modified slide glass; D is that oxidation zinc bar-polymer brush is modified slide glass; Scale in fluorescence photo is 0.5 mm; ).
Fig. 7 is the micro-array biochip three-dimensional carrier soaks 30 minutes front and back in 5 ug/ml fluorescins (the anti-goat IgG of CY3-) solution fluorescence photo.
Fig. 8 is that the micro-array biochip three-dimensional carrier adopts micro-array chip to detect to 10% serum sample of tumor markers CEA fluorescence photo and the typical curve that obtains.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
The micro-array biochip three-dimensional carrier, its structure and preparation technology are as shown in Figure 1.
As shown in Figure 1, the micro-array biochip three-dimensional carrier is by the zinc oxide nano rod of substrate material surface growing high density, random orientation, then gets at zinc oxide nano rod surface growth polymer brush.The growing polymer brush can pass through surperficial Atom Transfer Radical Polymerization (Surface-initiated Atom Transfer Radical Polymerization, SI-ATRP) technology.
The preparation method of micro-array biochip three-dimensional carrier, concrete steps are as follows:
A. clean slide is immersed in 5 mM and newly prepared potassium permanganate solution 20 minutes, take out and use deionized water rinsing; Then slide glass is put into and is contained 5%(v/v) thanomin and 5%(v/v) 50 mM zinc nitrate solutions of ammoniacal liquor, growth is 50 minutes under 85 ℃ of water-baths, make slide surface form zinc oxide nano rod, taking-up is dry after with deionized water rinsing, then observe with scanning electron, result as shown in Figure 2;
B. the slide glass after step a being processed is immersed in the ethanolic soln that contains 3% (v/v) 3-glycidoxypropyl trimethoxysilane (APTES) and soaked 2 hours, make 3-glycidoxypropyl trimethoxysilane and zinc oxide nano rod form silicon-oxygen covalent linkage, with the modification zinc oxide nanorod surfaces, after alcohol flushing, vacuum annealing is 2 hours at 110 ℃ of temperature;
C. the slide glass after step b processes is put into and is contained 0.35%(v/v) triethylamine (triethylamine, TEA) and α 0.6%(v/v)-bromine isobutyl acylbromide (2-bromoisobutyryl bromide, BIB) soaked 2 hours in dichloromethane solution, after taking out with dichloromethane rinse three times, to be connected into initiator on the zinc oxide nano rod surface;
d. will adopt through the slide glass that step c processes surperficial Atom Transfer Radical Polymerization technology that growing polymer brush on the slide glass of zinc oxide be arranged in this growth, be specially: first prepare 50 milliliters and contain 10%(v/v) oligomeric ethylene glycol methacrylic ester (oligo(ethylene glycol) methacrylate, OEGMA, molecular-weight average 360) and 0.4%(v/v) glycidyl methacrylate (glycidyl methacrylate, GMA) methanol/water (volume ratio is 1:1) solution, blast nitrogen 15-30 minute in solution, add again 150 milligram 2, 2'-dipyridyl (2, 2'-Dipyridyl) He 70 milligrams of cuprous bromides, after ultrasonic dissolution, the slide glass that step c is processed immerses rapidly, sealing solution and the inert atmosphere case of inserting lucifuge were preserved 12 hours, get the micro-array biochip three-dimensional carrier.Gained micro-array biochip three-dimensional carrier is observed under scanning electronic microscope and transmission electron microscope, result as shown in Figure 3 and Figure 4, by Fig. 3 and Fig. 4 as can be known, at gained micro-array biochip three-dimensional carrier, in slide surface growth, irregular zinc oxide nano rod is arranged, and formed polymer brush on the zinc oxide nano rod surface.
Carry out the infared spectrum analysis with what step c prepared in conjunction with the slide glass of zinc oxide nano rod and the three-dimensional carrier of steps d gained micro-array biochip, result as shown in Figure 5.In the surface growth of oxidation nanometer rod, polymer brush is arranged as can be known by infared spectrum, in the present embodiment, polymer brush is poly-(oligomeric ethylene glycol methacrylic ester-glycidyl methacrylate).
Embodiment 2
The preparation method of micro-array biochip three-dimensional carrier, concrete steps are as follows:
A. clean slide is immersed in 1 mM and newly prepared potassium permanganate solution 30 minutes, take out and use deionized water rinsing; Then slide glass is put into and is contained 1%(v/v) thanomin and 1%(v/v) 10 mM zinc nitrate solutions of strong aqua, growth is 60 minutes in 65 ℃ of water-baths, makes slide surface form zinc oxide nano rod, takes out with dry after deionized water rinsing;
B. the slide glass after step a being processed is immersed in and contains 1%(v/v) the ethanolic soln of 3-glycidoxypropyl trimethoxysilane (APTES) in soaked 3 hours, make 3-glycidoxypropyl trimethoxysilane and zinc oxide nano rod surface formation silicon-oxygen covalent linkage, with the modification zinc oxide nanorod surfaces, with after alcohol flushing at 110 ℃ of temperature, vacuum annealing 3 hours;
C. the slide glass after step b processes is put into and is contained 0.2%(v/v) triethylamine (triethylamine, TEA) and 0.4%(v/v) α-bromine isobutyl acylbromide (2-bromoisobutyryl bromide, BIB) soaked 2 hours in tetrahydrofuran solution, rinse three times with tetrahydrofuran (THF) after taking out, to be connected into initiator on the zinc oxide nano rod surface;
d. will adopt through the slide glass that step c processes surperficial Atom Transfer Radical Polymerization technology that growing polymer brush on the slide glass of zinc oxide be arranged in this growth, be specially: first prepare 50 milliliters and contain 30%(v/v) oligomeric ethylene glycol methacrylic ester (oligo (ethylene glycol) methacrylate, OEGMA, molecular-weight average 360) and 1%(v/v) glycidyl methacrylate (glycidyl methacrylate, GMA) methanol/water (volume ratio is 1:1) solution, add 230 milligram 2 again in solution, 2'-dipyridyl (2, 2 '-bipyridyl) and 170 milligrams of cupric bromides, then after the slide glass of step c being processed immerses, adding rapidly 1mL concentration is the aqueous ascorbic acid of 120mg/mL, wherein 2, 2'-dipyridyl and cupric bromide form complex compound Cu(II in solution)-2Bpy, this complex compound is reduced to cuprous complex compound Cu(I by xitix)-2Bpy, then at the surface catalysis Atom Transfer Radical Polymerization.Seal and the solution that vibrates, then insert the inert atmosphere case of lucifuge and preserved 12 hours, get the three-dimensional carrier of micro-array biochip.
Embodiment 3
The preparation method of the three-dimensional carrier of micro-array biochip, concrete steps are as follows:
A. clean slide is immersed in 10 mM and newly prepared potassium permanganate solution 15 minutes, take out and use deionized water rinsing; Then slide glass is put into and is contained 0.25%(v/v) thanomin and 5%(v/v) 100 mM zinc nitrate solutions of strong aqua, growth is 60 minutes in 95 ℃ of water-baths, make slide surface form zinc oxide nano rod, taking-up is dry after with deionized water rinsing, then observe with scanning electron, result as shown in Figure 2;
B. the slide glass after step a being processed is immersed in and contains 5%(v/v) soaked 1 hour in the ethanolic soln of 3-glycidoxypropyl trimethoxysilane (APTES), make 3-glycidoxypropyl trimethoxysilane and zinc oxide nano rod surface formation silicon-oxygen covalent linkage, with the modification zinc oxide nanorod surfaces, with vacuum annealing 1 hour at 110 ℃ of temperature after alcohol flushing;
C. the slide glass after step b processes is put into and is contained 0.4%(v/v) triethylamine (triethylamine, TEA) and 0.4%(v/v) α-bromine isobutyl acylbromide (2-bromoisobutyryl bromide, BIB) soaked 2 hours in dichloromethane solution, after taking out with dichloromethane rinse three times, to be connected into initiator on the zinc oxide nano rod surface;
d. the slide glass after step c processes is adopted surperficial Atom Transfer Radical Polymerization technology that growing polymer brush on the slide glass of zinc oxide is arranged in this growth, be specially: first prepare 50 milliliters and contain 20%(v/v) oligomeric ethylene glycol methacrylic ester (oligo(ethylene glycol) methacrylate, OEGMA, molecular-weight average 360) and the glycidyl methacrylate of 0.8% (v/v) (glycidyl methacrylate, GMA) methanol/water (volume ratio is 1:1) solution, blast nitrogen 15-30 minute in solution, add again 150 milligram 2, 2'-dipyridyl (2, 2 '-Dipyridyl) and 70 milligrams of cuprous bromides, after ultrasonic dissolution, the slide glass of step c gained in conjunction with zinc oxide nano rod immersed rapidly, sealing solution and the inert atmosphere case of inserting lucifuge were preserved 10 hours, get the three-dimensional carrier of micro-array biochip.
Embodiment 4
Biochip preparation and detecting step:
The anti-goat IgG (anti-Goat IgG) of probe molecule CY3 mark is dissolved in 0.01M PBS solution, make the solution that concentration is 800 μ g/mL, adopt micro-array chip point sample instrument (contact point sample or contactless spot sample mode all can) at the three-dimensional carrier surface printing microarray of embodiment 1 preparation, after point sample with three-dimensional carrier under room temperature 20-25 ℃ standing 8-12 hour, with carrying out fluorescent scanning after the cleaning of 0.01M PBS solution, drying, scanning result is as shown in Fig. 6 d again.Then adopt same solution at the microarray of other carrier surface printings, then carry out fluorescent scanning, wherein Fig. 6 a is at epoxy activation slide surface printing microarray; Fig. 6 b modifies slide surface printing microarray at poly-(oligomeric ethylene glycol methacrylic ester-glycidyl methacrylate) polymer brush; Fig. 6 c modifies the microarray of slide surface printing at epoxy active oxidation zinc bar.The microarray of the three-dimensional carrier preparation that the present invention is obtained is compared with the microarray of other carriers preparations, and the fluorescence intensity that obtains on the three-dimensional carrier of the present invention's preparation obviously strengthens, and each little some even intensity, shape standard.Therefore, use three-dimensional carrier of the present invention can make the protein probe molecular density be fixed in the three-dimensional carrier surface, be conducive to the detection of micro-array chip.
Be submergence 30 minutes in the anti-goat IgG solution of 5 μ g/mLCY3 marks with the three-dimensional carrier of the micro-array biochip of embodiment 1 preparation in concentration, with carrying out fluorescent scanning after the cleaning of 0.01M PBS solution, drying, get fluorescence photo shown in Fig. 7 b after taking out.(Fig. 7 a), the fluorescence intensity of this three-dimensional carrier has proved that the three-dimensional carrier of the present invention's preparation is highly resistant to nonspecific proteins absorption under solution condition, for the highly selective immunodetection provides assurance without obvious rising to compare fluorescence photo before soaking.
The anticancer embryonal antigen monoclonal antibody of probe molecule (monoclonal anti-CEA) is dissolved in 0.01M PBS solution, make the solution that concentration is 800 μ g/mL, adopt the micro-array chip point sample instrument at the three-dimensional carrier surface printing microarray of the micro-array biochip of embodiment 1 preparation, after point sample with three-dimensional carrier at room temperature standing 8-12 hour, then with 0.01M PBS solution clean, drying.Then adopt sandwich assay to tumor markers carcinomebryonic antigen (carcino-embryonic antigen, CEA) detect, namely first chip was reacted 1 hour with the 10% human serum solution soaking that contains different concns CEA respectively, again with polyclonal antibody (the polyclonal anti-CEA of anticancer embryonal antigen, produced in Mouse) reaction is 30 minutes, the anti-mouse IgG reaction of last and CY3 mark 15 minutes, dry after cleaning, then adopt the fluorescent scanning instrument that chip signal is read, get fluorescence photo shown in Fig. 8 a.The intensity of fluorescent signal is used for the drawing standard curve, as shown in Fig. 8 b.Obtained to reach 100pg/mL based on micro-array chip detectability to CEA in human serum of this three-dimensional carrier by typical curve, so detection sensitivity is high, has excellent performance.
Explanation is at last, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can make various changes to it in the form and details, and not depart from claims limited range of the present invention.
Claims (10)
1. the three-dimensional carrier of micro-array biochip, it is characterized in that: the three-dimensional carrier of described micro-array biochip is at the substrate material surface growing zinc oxide nanorod, then gets at zinc oxide nano rod surface growth polymer brush.
2. micro-array biochip three-dimensional carrier according to claim 1, it is characterized in that: described base material is sheet glass, plastic sheet, nylon membrane or silicon chip.
3. micro-array biochip three-dimensional carrier according to claim 1 is characterized in that: described polymer brush is poly-(oligomeric ethylene glycol methacrylic ester-glycidyl methacrylate).
4. the described micro-array biochip three-dimensional carrier of according to claim 1 to 3 any one, is characterized in that: the surperficial Atom Transfer Radical Polymerization technology growth of described polymer brush employing.
5. the preparation method of the described micro-array biochip three-dimensional carrier of claim 1 to 4 any one, is characterized in that, comprises the steps:
A. the surface with base material activates, then at the substrate material surface growing zinc oxide nanorod;
B. the zinc oxide nano rod with growth carries out finishing;
C. the zinc oxide nano rod surface after modification is connected into initiator;
D. be connected into the zinc oxide nano rod surface growth polymer brush of initiator, getting the three-dimensional carrier of micro-array biochip.
6. preparation method according to claim 5 is characterized in that: in described step a, described activation is to be that 1-10mM potassium permanganate soaked 15-30 minute with base material concentration.
7. preparation method according to claim 5, it is characterized in that: in described step a, described growing zinc oxide nanorod is that the base material of activation is put into the mixing solutions that contains thanomin, ammoniacal liquor and zinc nitrate, growth is 30-60 minute in 65-95 ℃ of water-bath, in described mixing solutions, the final concentration of zinc nitrate is 10-100mM, the volume fraction of thanomin is 1-10%, and the volume fraction of ammoniacal liquor is 1-10%.
8. preparation method according to claim 5, it is characterized in that: described step b is immersed in the base material after step a processing in the ethanolic soln that contains the 3-glycidoxypropyl trimethoxysilane to soak 1-3 hour, then with after alcohol flushing, at 110 ℃ of temperature vacuum annealing 1-3 hour; In the ethanolic soln of the described 3-of containing glycidoxypropyl trimethoxysilane, the volumetric concentration of 3-glycidoxypropyl trimethoxysilane is 1%-5%.
9. preparation method according to claim 5, it is characterized in that: described step c is that the base material after step b is processed was put into the tetrahydrofuran solution that contains triethylamine and α-bromine isobutyl acylbromide or dichloromethane solution 2 hours, after taking out with tetrahydrofuran (THF) or dichloromethane rinse; In described tetrahydrofuran solution, the volume fraction of triethylamine is 0.2%-0.4%, and the volume fraction of α-bromine isobutyl acylbromide is 0.4%-0.6%.
10. according to claim 5-9 described preparation methods of any one, is characterized in that: the zinc oxide nano rod surperficial employing surperficial Atom Transfer Radical Polymerization technology growth polymer brush of described steps d for being connected into initiator.
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| CN107486270B (en) * | 2017-08-08 | 2020-10-23 | 上海格荣生物科技有限公司 | Preparation method of microarray chip based on ball-brush double-layer nanostructure substrate |
| CN110702642A (en) * | 2019-10-29 | 2020-01-17 | 西南大学 | Preparation method of micro-well structured SPRi chip, product and application thereof |
| CN110702642B (en) * | 2019-10-29 | 2022-03-18 | 西南大学 | Preparation method of micro-well structured SPRi chip, product and application thereof |
| CN113447446A (en) * | 2021-06-28 | 2021-09-28 | 西南大学 | Chip for quantitatively detecting reductive multi-component biomolecular substances by utilizing oblique incidence light reflection difference and application and detection method |
| CN114460047A (en) * | 2021-12-20 | 2022-05-10 | 上海中医药大学 | Artificial modified 3D photo-crosslinking probe and method for fishing Chinese herbal medicine active small-molecule synthetase |
| CN114904595A (en) * | 2022-06-21 | 2022-08-16 | 中国科学院长春应用化学研究所 | Microarray chip based on gold nanorod-brush double-layer nanostructure substrate and preparation method thereof |
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