CN104152897A - Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film - Google Patents
Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film Download PDFInfo
- Publication number
- CN104152897A CN104152897A CN201410404019.2A CN201410404019A CN104152897A CN 104152897 A CN104152897 A CN 104152897A CN 201410404019 A CN201410404019 A CN 201410404019A CN 104152897 A CN104152897 A CN 104152897A
- Authority
- CN
- China
- Prior art keywords
- gold nanorods
- preparation
- aqueous solution
- ctab
- sers substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 69
- 239000000758 substrate Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002356 single layer Substances 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000007864 aqueous solution Substances 0.000 claims abstract description 62
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000523 sample Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 37
- -1 mercapto alkane Chemical class 0.000 claims description 33
- 238000001338 self-assembly Methods 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006073 displacement reaction Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 238000003491 array Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ZVEZMVFBMOOHAT-UHFFFAOYSA-N nonane-1-thiol Chemical compound CCCCCCCCCS ZVEZMVFBMOOHAT-UHFFFAOYSA-N 0.000 claims description 2
- CCIDWXHLGNEQSL-UHFFFAOYSA-N undecane-1-thiol Chemical compound CCCCCCCCCCCS CCIDWXHLGNEQSL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 22
- 239000003446 ligand Substances 0.000 abstract description 10
- 230000002708 enhancing effect Effects 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract 3
- 238000006467 substitution reaction Methods 0.000 abstract 3
- 238000001069 Raman spectroscopy Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for manufacturing an SERS substrate monolayer film. The method comprises the following steps that (1) gold nanorod aqueous solutions with the length-diameter ratio of 3.8 to 4.2 are prepared; (2) the gold nanorod aqueous solutions are centrifugalized, and then are redissolved and dispersed in CTAB aqueous solutions, and the concentration ratio of gold nanorods to CTAB in the obtained gold nanorod CTAB aqueous solutions is 1 to 3:100; (3) sulfydryl alkane ethanol solutions are prepared, the sulfydryl alkane ethanol solutions are dropwise added into the gold nanorod CTAB aqueous solutions prepared in the step (2), the volume ratio of the sulfydryl alkane ethanol solutions to the gold nanorod CTAB aqueous solutions is 1:9 to 10, the sulfydryl alkane ethanol solutions and the gold nanorod CTAB aqueous solutions are sufficiently stirred, and ligand substitution mixed solutions are obtained; (4) organic solvents are added into the ligand substitution mixed solutions, the volume ratio of the organic solvents to the ligand substitution mixed solutions is 1.1 to 1.5:1, standing is carried out on a sample, and the SERS substrate monolayer film is obtained from a water phase upper surface. The invention further discloses the SERS substrate monolayer film manufactured by the method, and the SERS substrate monolayer film is high in stability, good in enhancing effect, strong in reproducibility and capable of being used for detecting biological probe molecules.
Description
Technical field
The present invention relates to a kind of preparation method and this SERS substrate unitary film of SERS substrate unitary film, be specifically related to by utilize preparation method and this SERS substrate unitary film of a kind of SERS substrate unitary film that gold nanorods self-assembly carries out at steam interface.
Background technology
Raman spectrum is the harmless analytical technology of a kind of noncontact, and its interaction based on chemical bond in light and material produces.Raman spectrum can sampling chemical structure, the details of phase and form, crystallization and interaction of molecules.But in the ordinary course of things, its strength of signal very a little less than, limited its range of application.How increasing its spectral intensity is the key issue in raman study.Surface enhanced Raman scattering (SERS) technology has overcome the shortcoming of the inherent weak output signal of traditional Raman spectrum, can so that Raman enhancement factor up to 10
14-10
15, there is high sensitivity, be a kind of Analytical Methods of Trace of powerful detection analytes in low concentration, even can realize Single Molecule Detection.Therefore in fields such as chemistry, biology, environment, be, all very important analysis means.In recent years, along with the research that deepens continuously to nano material self-assembling technique, utilize the research of nano material self-assembly SERS substrate also to become an important branch of SERS.
At present, the SERS mechanism that academia generally admits mainly contains physics enhanced mechanism and chemical enhanced mechanism two classes.The active surface of SERS often can produce the local electric field of enhancing, is that metal surface plasma resonance causes, this is called as physics and strengthens; The transfer that the absorption of molecule on metal is often accompanied by electric charge causes the variation of molecular entergy level, or molecular adsorption also causing strengthening on the system point of special metallic surface, and both of these case is all called as chemistry to be strengthened.It is that a few metals such as gold and silver, copper and substrate surface are coarse that yet SERS requires substrate, and this has limited the application of SERS technology greatly.The Problem of Universality of base material and pattern is the key issue of restriction SERS technical development always.
Patent CN103604798A discloses the method that the anion modified nanoparticle of a kind of use strengthens Raman spectrum, and it take metal nanoparticle as kernel, and the strong negatively charged ion adsorbing of the full individual layer of take is decorative layer, thereby the nanoparticle that obtains surface modification is as SERS substrate.Patent CN102706856A discloses a kind of enhancing raman nanoparticle and preparation method thereof, and it wraps up a strata Dopamine HCL in surfaces of metal nanoparticles, for preventing and treating probe, pollutes.Existing enhancing substrate cannot obtain the metal nanoparticle of uniform surface, the method of preparing metal nanoparticle SERS substrate is mainly by gold nanorods solution is dripped on substrate, after solvent evaporates is complete, remaining gold nanorods forms metal nano-rod substrate on substrate.But, the SERS substrate small scale (below tens microns) that this method obtains, structure intersperses among on substrate discontinuous, cannot locate, and presents on the whole unordered state, does not also obtain excellent sensitivity.
As can be seen here, how preparing uniform surface, highly sensitive metal nanoparticle, to strengthen substrate be a challenge of this area.Seek the enhancing system that a kind of stability is high, reinforced effects good, circulation ratio is strong, realizing in nanoparticle assembly the particle diameter of particle and the controllability of distribution thereof and homogeneity is the key of constructing SERS active substrate.
Summary of the invention
One of object of the present invention is to provide a kind of preparation method of SERS substrate unitary film, and it can realize the particle diameter of particle and the controllability of distribution and homogeneity in nanoparticle assembly
For reaching this object, the present invention by the following technical solutions:
A preparation method for SERS substrate unitary film, is characterized in that, comprises the following steps:
1) prepare the gold nanorods aqueous solution that length-to-diameter ratio is 3.8-4.2;
2) the gold nanorods aqueous solution is centrifugal, then redissolve and to be dispersed in the CTAB aqueous solution, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 1-3:1000;
3) ethanolic soln of preparation mercapto alkane; Described mercapto alkane ethanolic soln is dropped to step 2) in the gold nanorods CTAB aqueous solution prepared, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:9-10; Fully stir part displacement mixing solutions;
4) add organic solvent, the volume ratio of described organic solvent and described part displacement mixing solutions is 1.1-1.5:1, and standing sample, makes described SERS substrate unitary film at water upper surface.
Utilize thus gold nanorods at the unitary film that is self-assembled into extensive ordered arrangement at steam interface, a kind of efficient assembling SERS method of substrate is provided.
Preferably, in step 1) in, the method for preparing the described aqueous solution is seed flop-in method.
In step 2) in, the concentration 1 * 10 of the described CTAB aqueous solution
-6molL
-1-15 * 10
-6molL
-1, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 1-3:1000, realizes the preliminary modification to gold nanorods in the CTAB of the lower concentration aqueous solution.And if gold nanorods occurs that irreversible reunion must reconfigure in this process;
In step 3) in, certain density mercapto alkane solution prepared, so that it can successfully replace the CTAB that is connected to gold nanorods surface in next step; Described mercapto alkane is that carbonatoms is the alkyl sulfhydryl of 9-12, and preferably, it is the mixture of a kind of in nonyl mercaptan, decyl mercaptan, undecyl mercaptan and lauryl mercaptan or at least two kinds; Mercapto alkane solution is joined gradually in the gold nanorods CTAB aqueous solution of high-speed stirring, fully stir, and keep time enough to make mercapto alkane can replace gold nanorods surface ligand CTAB.Preferably, the rotating speed of described stirring is 600r/min-800r/min; The time of described stirring is 1-6min.
In step 4) in, add organic solvent, impel gold nanorods to transfer to water upper surface and evenly arrange.Standing sample, gold nanorods pools a carvel-built film at water upper surface.Described organic solvent be density ratio water large and with the immiscible organic solvent of water, preferably chloroform and/or methylene dichloride.
According to above-mentioned steps, prepare self-assembly SERS substrate unitary film, by controlling step 3) in the concentration of mercapto alkane solution can regulate and control the self-assembly mode of GOLD FROM PLATING SOLUTION nanometer rod and the orientation of SERS substrate unitary film.It has two kinds aligned, tiling orientation and vertical orientated.The corresponding gold nanorods tiling self-assembly SER substrate unitary film of two kinds of different aligned difference and gold nanorods orthogonal array self-assembly SERS substrate unitary film.
In step 3) in, while configuring the ethanolic soln of described mercapto alkane, the volume ratio of mercapto alkane and ethanol is 1-2:8-9, preferably 2:7.Thereby make gold nanorods tiling self-assembly SERS substrate unitary film.
Another object of the present invention is to thus provide a kind of gold nanorods tiling self-assembly SER substrate unitary film of preparing according to aforesaid method, described SERS substrate unitary film has gold nanorods tiled arrays, film forming area approximately 3.7 μ m * 3.7 μ m, gold nanorods spacing is about 1-2.5nm, and the tiling orientation rate of gold nanorods is about 93%-96%.This little interrod spacing has caused the strong coupling of plasma oscillation between gold nanorods, makes site have Raman reinforced effects.The tiling orientation rate of gold nanorods is about 93%-96%.
Or, in step 3) in, while configuring the ethanolic soln of described mercapto alkane, the volume ratio of mercapto alkane and ethanol is 3-5:5-7, preferably 5:7.Thereby make gold nanorods orthogonal array self-assembly SERS substrate unitary film.
The another object of invention is to provide a kind of gold nanorods orthogonal array self-assembly SERS substrate unitary film of preparing according to aforesaid method thus, described SERS substrate unitary film has gold nanorods orthogonal array, film forming area approximately 4 μ m * 4 μ m, gold nanorods spacing is about 1-2.5nm, and the vertical orientated rate of gold nanorods is about 95%-98%.Use respectively two kinds of SERE substrate unitary films prepared by different concns mercapto alkane ethanolic soln to there is almost consistent gold nanorods trend rate, guaranteed the spatial uniformity of Raman enhancement factor.Utilize the membrane area of SERS substrate unitary film prepared by this self-assembling method large, planeness is good, and homogeneity is high
The present invention also aims to provide described gold nanorods tiling self-assembly SERS substrate unitary film and the purposes of gold nanorods orthogonal array self-assembly SERS substrate unitary film in detection of biological probe molecule.By orthogonal array self-assembly SERS substrate unitary film of the present invention, for detection of probe molecule rhodamine 6G, this SERS basal signal strengthens high, and Raman peaks is strong, there is good resolution, and the concentration of probe molecule and Raman enhancing intensity are done to figure, and find that its linearity is wide, highly sensitive.
The invention provides a kind of preparation method of SERS substrate unitary film, the SERS film forming area of preparation is large thus, can reach 4 μ m * 4 μ m; Interrod spacing is little, is only 1-2.5nm, has caused the strong coupling of plasma oscillation between gold nanorods, causes site to have Raman reinforced effects; Orientation rate can reach 98%, and almost consistent gold nanorods trend rate, has guaranteed the spatial uniformity of Raman enhancement factor, thereby can realize the particle diameter of particle and the controllability of distribution and homogeneity in nanoparticle assembly.Described SERS substrate unitary film is for detection of bioprobe molecule, and this SERS basal signal strengthens high, and Raman peaks is strong, have good resolution, the concentration of bioprobe molecule and Raman strengthen intensity and present good linear relationship, reproducible, highly sensitive, linearity range is wide.
Accompanying drawing explanation
Fig. 1 is gold nanorods tiling self-assembly SERS substrate unitary film schematic diagram of the present invention.
Fig. 2 is the electron scanning micrograph of gold nanorods tiling self-assembly SERS substrate unitary film of the present invention.
Fig. 3 is the vertical self-assembly SERS of gold nanorods of the present invention substrate unitary film schematic diagram.
Fig. 4 is the electron scanning micrograph of the vertical self-assembly SERS of gold nanorods of the present invention substrate unitary film.
Fig. 5 is that rhodamine 6G is at the suprabasil Raman signal intensity figure of SERS.
Fig. 6 is that rhodamine 6G is at the linear relationship chart of the suprabasil strength of signal of SERS and its concentration logarithm.
Embodiment
Below in conjunction with accompanying drawing and by embodiment, further illustrate technical scheme of the present invention.
Embodiment 1: the preparation method of gold nanorods tiling self-assembly SERS substrate unitary film
Using seed mediated growth method to prepare length-to-diameter ratio is 3.8 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 1 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 1:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 1:9.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 600r/min rotating speed, at the uniform velocity stir 1 minute, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:9, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is 1.1:1, and the gold nanorods that impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes gold nanorods pool a carvel-built film at water upper surface.
Embodiment 2
Using seed mediated growth method to prepare length-to-diameter ratio is 4.2 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 15 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 3:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 1:4.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 800r/min rotating speed, at the uniform velocity stir 6 minutes, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:10, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is 1.5:1, and the gold nanorods that impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes gold nanorods pool a carvel-built film at water upper surface.
Embodiment 3
Using seed mediated growth method to prepare length-to-diameter ratio is 4.0 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 8 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 2:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 2:7.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 700r/min rotating speed, at the uniform velocity stir 4 minutes, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:9, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is 1.1:1, and the gold nanorods that impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes gold nanorods pool a carvel-built film at water upper surface.Its schematic diagram is as Fig. 1, and electron scanning micrograph is as Fig. 2.By detecting, its film forming area approximately 3.7 μ m * 3.7 μ m, gold nanorods spacing is about 1-2.5nm, and this little interrod spacing has caused the strong coupling of plasma oscillation between gold nanorods, makes site have Raman reinforced effects.The tiling orientation rate of gold nanorods is about 93%-96%, and consistent gold nanorods trend rate has almost guaranteed the spatial uniformity of Raman enhancement factor.The membrane area that utilizes this self-assembling method to prepare is large, and planeness is good, and homogeneity is high.
Embodiment 4: the preparation method of the vertical self-assembly SERS of gold nanorods substrate unitary film
Using seed mediated growth method to prepare length-to-diameter ratio is 3.8 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 1 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 1:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 3:7.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 600r/min rotating speed, at the uniform velocity stir 1 minute, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:9, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is 1.1:1, and the gold nanorods that impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes GNR pool a carvel-built film at water upper surface.
Embodiment 5
Using seed mediated growth method to prepare length-to-diameter ratio is 4.2 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 15 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 3:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 1:1.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 800r/min rotating speed, at the uniform velocity stir 6 minutes, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:10, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is that the gold nanorods that 1.5:1 impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes gold nanorods pool a carvel-built film at water upper surface.
Embodiment 6
Using seed mediated growth method to prepare length-to-diameter ratio is 4.0 the gold nanorods aqueous solution.By the gold nanorods aqueous solution centrifugal concentrating of preparation, redispersion is in concentration approximately 8 * 10
-6molL
-1the CTAB aqueous solution in, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 2:1000, stand for standby use.Preparation part substitutional solution, i.e. mercapto alkane ethanolic soln, wherein the volume ratio of sulfydryl alkane and ethanol is about 5:7.Get the gold nanorods CTAB aqueous solution in sample bottle, drip sulfydryl alkane solution and under 700r/min rotating speed, at the uniform velocity stir 4 minutes, make it fully contact to carry out efficient ligand displacement with gold nanorods, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:10, obtains part displacement mixing solutions.Add chloroform, the volume ratio that itself and part are replaced mixing solutions is 1.1:1, and the gold nanorods that impels sulfydryl alkane to modify is transferred to water upper surface.Standing sample, makes gold nanorods pool a carvel-built film at water upper surface.Its schematic diagram is as Fig. 3, electron scanning micrograph is as Fig. 4, its film forming area approximately 4 μ m * 4 μ m, and gold nanorods spacing is about 1-2.5nm, this little interrod spacing has caused the strong coupling of plasma oscillation between gold nanorods, causes site to have Raman reinforced effects.The vertical orientated rate of gold nanorods is about 95%-98%, and this almost consistent gold nanorods trend rate has guaranteed the spatial uniformity of Raman enhancement factor.The membrane area that utilizes this self-assembling method to prepare is large, and planeness is good, and homogeneity is high, and interrod spacing is little, effectively improves the focus resonance effect between rod and rod.
Embodiment 7 detection of biological probe molecules
The vertical self-assembly SERS of the gold nanorods substrate unitary film detection probes molecule rhodamine 6G that uses embodiment 6 preparations, rhodamine 6G in the suprabasil Raman signal intensity of SERS as shown in Figure 5.Raman figure is known thus, and this SERS basal signal strengthens high, and Raman peaks is strong, has good resolution.And the concentration of probe molecule and Raman enhancing intensity are done to figure, find that its concentration logarithm and Raman strengthen intensity and become good linear relationship, as shown in Figure 6, its linearity is wide, highly sensitive, illustrate that this SERS base unitary film activity is high, good uniformity, be applicable to detect in high sensitivity the bioprobe molecule of lower concentration, and be hopeful to be applied to and in other biological system, carry out high-sensitive biological detection.
The invention provides a kind of preparation method of SERS substrate unitary film, the real a kind of stability of the SERS substrate unitary film of preparation is high thus, reinforced effects good, circulation ratio is strong.Can realize the particle diameter of particle and the controllability of distribution and homogeneity in nanoparticle assembly.Described SERS substrate unitary film is for detection of bioprobe molecule, and the concentration of bioprobe molecule and Raman strengthen intensity and present good linear relationship, and reproducible, highly sensitive, linearity range is wide.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for SERS substrate unitary film, is characterized in that, comprises the following steps:
1) prepare the gold nanorods aqueous solution that length-to-diameter ratio is 3.8-4.2;
2) the gold nanorods aqueous solution is centrifugal, then redissolve and to be dispersed in the CTAB aqueous solution, in the gold nanorods CTAB aqueous solution of gained, the concentration ratio of gold nanorods and CTAB is 1-3:1000;
3) ethanolic soln of preparation mercapto alkane; Described mercapto alkane ethanolic soln is dropped to step 2) in the gold nanorods CTAB aqueous solution prepared, the volume ratio of described mercapto alkane ethanolic soln and the gold nanorods CTAB aqueous solution is 1:9-10, fully stirs, and makes part displacement mixing solutions;
4) add organic solvent, the volume ratio of described organic solvent and described part displacement mixing solutions is 1.1-1.5:1, and standing sample, makes described SERS substrate unitary film at water upper surface.
2. preparation method according to claim 1, is characterized in that, in step 1) in preparation the described aqueous solution method be seed flop-in method.
3. preparation method according to claim 1 and 2, is characterized in that, in step 2) in, the concentration 1 * 10 of the described CTAB aqueous solution
-6molL
-1-15 * 10
-6molL
-1.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that, in step 3) in, described mercapto alkane is that carbonatoms is the alkyl sulfhydryl of 9-12, preferably, it is the mixture of a kind of in nonyl mercaptan, decyl mercaptan, undecyl mercaptan and lauryl mercaptan or at least two kinds;
Preferably, the rotating speed of described stirring is 600r/min-800r/min;
Preferably, the time of described stirring is 1-6min.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that, in step 4) in, described organic solvent is chloroform and/or methylene dichloride.
6. according to the preparation method described in claim 1-5 any one, it is characterized in that, in step 3) in, while configuring the ethanolic soln of described mercapto alkane, the volume ratio of mercapto alkane and ethanol is 1-2:8-9, preferred 2:7, thus make gold nanorods tiling self-assembly SERS substrate unitary film.
7. according to the preparation method described in claim 1-5 any one, it is characterized in that, in step 3) in, while configuring the ethanolic soln of described mercapto alkane, the volume ratio of mercapto alkane and ethanol is 3-5:5-7, preferred 5:7, thus make the vertical self-assembly SERS of gold nanorods substrate unitary film.
8. the gold nanorods tiling self-assembly SER substrate unitary film that prepared by preparation method according to claim 6, it is characterized in that, described SERS substrate unitary film has gold nanorods tiled arrays, film forming area approximately 3.7 μ m * 3.7 μ m, gold nanorods spacing is about 1-2.5nm, and the tiling orientation rate of gold nanorods is about 93%-96%.
9. the vertical self-assembly SERS of the gold nanorods substrate unitary film that prepared by preparation method according to claim 7, it is characterized in that, described SERS substrate unitary film has gold nanorods orthogonal array, film forming area approximately 4 μ m * 4 μ m, gold nanorods spacing is about 1-2.5nm, and the vertical orientated rate of gold nanorods is about 95%-98%.
10. the SERS substrate unitary film according to claim 8 or claim 9 purposes in detection of biological probe molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410404019.2A CN104152897B (en) | 2014-08-15 | 2014-08-15 | Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410404019.2A CN104152897B (en) | 2014-08-15 | 2014-08-15 | Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104152897A true CN104152897A (en) | 2014-11-19 |
| CN104152897B CN104152897B (en) | 2017-02-08 |
Family
ID=51878516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410404019.2A Expired - Fee Related CN104152897B (en) | 2014-08-15 | 2014-08-15 | Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104152897B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104999071A (en) * | 2015-06-24 | 2015-10-28 | 深圳先进技术研究院 | Gold nanorod array and preparation method and application thereof |
| CN105712294A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Large-area gold nanorod aligned and ordered array, preparation method and application thereof |
| CN106082337A (en) * | 2016-06-08 | 2016-11-09 | 中国科学院合肥物质科学研究院 | VO2(M) nanometer line ordered array and preparation method thereof |
| CN106882764A (en) * | 2017-02-16 | 2017-06-23 | 华东理工大学 | A kind of preparation method of the water phase gold nanorods assembly based on host-guest interaction |
| CN106929838A (en) * | 2015-12-31 | 2017-07-07 | 北京大学 | The method that preparation is suitable to the enhancing substrate of cell surface bio-orthogonal Raman image |
| CN109834292A (en) * | 2019-04-11 | 2019-06-04 | 中国科学院宁波材料技术与工程研究所 | Macroscopical large-area two-dimensional Janus nano-gold film and the preparation method and application thereof |
| CN109856117A (en) * | 2019-03-29 | 2019-06-07 | 上海应用技术大学 | The detection method of ampicillin antibiotic in a kind of water body |
| CN110108697A (en) * | 2019-06-25 | 2019-08-09 | 北威(重庆)科技股份有限公司 | Surface enhanced Raman scattering micro-nano chip and preparation method thereof, application and Raman spectrum test macro |
| CN110261367A (en) * | 2019-07-10 | 2019-09-20 | 中国科学技术大学 | A kind of SERS substrate, preparation method, regulate and control SERS substrate hotspot architecture method and SERS substrate application |
| CN111198175A (en) * | 2018-11-19 | 2020-05-26 | 中国科学院宁波材料技术与工程研究所 | Macroscopic large-area nano gold rod two-dimensional array with controllable distribution of hot spots and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506629A (en) * | 2012-06-18 | 2014-01-15 | 国家纳米科学中心 | Gold nanorod vertical array and preparing method thereof |
-
2014
- 2014-08-15 CN CN201410404019.2A patent/CN104152897B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506629A (en) * | 2012-06-18 | 2014-01-15 | 国家纳米科学中心 | Gold nanorod vertical array and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| WENBO WEI: "Monolayer of Nanord Vertical Arrays self-assembled at the air/water interface", 《PARTICLE & PARTICLE SYTEMS CHARACTERIZATION》 * |
| YONG XIE ET AL: "Self-Assembly of Gold Nanords into Symmetric Superlattices Directed by OH-Terminated Hexa(ethylene glycol) Alkanethiol", 《LANGMUIR》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712294B (en) * | 2014-12-05 | 2017-12-08 | 中国科学院宁波材料技术与工程研究所 | The oriented and ordered array of nanometer gold bar large area, its preparation method and application |
| CN105712294A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Large-area gold nanorod aligned and ordered array, preparation method and application thereof |
| CN104999071B (en) * | 2015-06-24 | 2017-04-05 | 深圳先进技术研究院 | A kind of gold nano stick array and its preparation method and application |
| CN104999071A (en) * | 2015-06-24 | 2015-10-28 | 深圳先进技术研究院 | Gold nanorod array and preparation method and application thereof |
| CN106929838A (en) * | 2015-12-31 | 2017-07-07 | 北京大学 | The method that preparation is suitable to the enhancing substrate of cell surface bio-orthogonal Raman image |
| CN106082337A (en) * | 2016-06-08 | 2016-11-09 | 中国科学院合肥物质科学研究院 | VO2(M) nanometer line ordered array and preparation method thereof |
| CN106882764A (en) * | 2017-02-16 | 2017-06-23 | 华东理工大学 | A kind of preparation method of the water phase gold nanorods assembly based on host-guest interaction |
| CN111198175A (en) * | 2018-11-19 | 2020-05-26 | 中国科学院宁波材料技术与工程研究所 | Macroscopic large-area nano gold rod two-dimensional array with controllable distribution of hot spots and application |
| CN111198175B (en) * | 2018-11-19 | 2022-09-27 | 中国科学院宁波材料技术与工程研究所 | Macroscopic large-area nano gold rod two-dimensional array with controllable distribution of hot spots and application |
| CN109856117A (en) * | 2019-03-29 | 2019-06-07 | 上海应用技术大学 | The detection method of ampicillin antibiotic in a kind of water body |
| CN109834292A (en) * | 2019-04-11 | 2019-06-04 | 中国科学院宁波材料技术与工程研究所 | Macroscopical large-area two-dimensional Janus nano-gold film and the preparation method and application thereof |
| CN109834292B (en) * | 2019-04-11 | 2021-11-23 | 中国科学院宁波材料技术与工程研究所 | Macroscopic large-area two-dimensional Janus nano gold film and preparation method and application thereof |
| CN110108697A (en) * | 2019-06-25 | 2019-08-09 | 北威(重庆)科技股份有限公司 | Surface enhanced Raman scattering micro-nano chip and preparation method thereof, application and Raman spectrum test macro |
| CN110108697B (en) * | 2019-06-25 | 2022-03-08 | 北威(重庆)科技股份有限公司 | Surface-enhanced Raman scattering micro-nano chip, preparation method and application thereof, and Raman spectrum testing system |
| CN110261367A (en) * | 2019-07-10 | 2019-09-20 | 中国科学技术大学 | A kind of SERS substrate, preparation method, regulate and control SERS substrate hotspot architecture method and SERS substrate application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104152897B (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104152897A (en) | Method for manufacturing SERS substrate monolayer film and SERS substrate monolayer film | |
| Jin et al. | Ultralarge area sub-10 nm plasmonic nanogap array by block copolymer self-assembly for reliable high-sensitivity SERS | |
| Wei et al. | Fabrication of large-area arrays of vertically aligned gold nanorods | |
| Tan et al. | Direct observation of interactions between nanoparticles and nanoparticle self-assembly in solution | |
| Zhan et al. | Single-molecule plasmonic optical trapping | |
| Gao et al. | Light trapping induced flexible wrinkled nanocone SERS substrate for highly sensitive explosive detection | |
| Wang et al. | Monodisperse, micrometer-scale, highly crystalline, nanotextured Ag dendrites: rapid, large-scale, wet-chemical synthesis and their application as SERS substrates | |
| Xu et al. | Facile detection of polycyclic aromatic hydrocarbons by a surface-enhanced Raman scattering sensor based on the Au coffee ring effect | |
| Wang et al. | Experimental observation of giant chiroptical amplification of small chiral molecules by gold nanosphere clusters | |
| CN103127890B (en) | Raman strengthening active microsphere and preparation method and application thereof | |
| Lu et al. | Mixing assisted “hot spots” occupying SERS strategy for highly sensitive in situ study | |
| Ahmadivand et al. | Directional toroidal dipoles driven by oblique poloidal and loop current flows in plasmonic meta-atoms | |
| Wang et al. | High-performance flexible surface-enhanced Raman scattering substrates fabricated by depositing Ag nanoislands on the dragonfly wing | |
| Yang et al. | One-step preparation method of flexible metafilms on the water–oil interface: self-assembly surface plasmon structures for surface-enhanced Raman scattering detection | |
| CN102608093A (en) | Detection method of polycyclic aromatic hydrocarbons (PAHs) | |
| Su et al. | Surface-enhanced Raman spectroscopy study on the structure changes of 4-Mercaptophenylboronic Acid under different pH conditions | |
| Ahmed et al. | Monolayer assembly of MultiSpiked gold nanoparticles for surface-enhanced Raman spectroscopy-based trace detection of dyes and explosives | |
| Metzger et al. | Dynamic spin-controlled enantioselective catalytic chiral reactions | |
| Xia et al. | Ag nanocubes monolayer-modified PDMS as flexible SERS substrates for pesticides sensing | |
| Liusman et al. | Surface-enhanced Raman scattering of Ag–Au nanodisk heterodimers | |
| He et al. | Silver porous nanotube built three-dimensional films with structural tunability based on the nanofiber template-plasma etching strategy | |
| Dai et al. | Obviously angular, cuboid-shaped TiO2 nanowire arrays decorated with Ag nanoparticle as ultrasensitive 3D surface-enhanced Raman scattering substrates | |
| Kamandi et al. | Unscrambling structured chirality with structured light at the nanoscale using photoinduced force | |
| Zhang et al. | Surfactant-free interface suspended gold graphitic surface-enhanced Raman spectroscopy substrate for simultaneous multiphase analysis | |
| Jiang et al. | Recyclable and green AuBPs@ MoS2@ tinfoil box for high throughput SERS tracking of diquat in complex compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170208 |