CN102590176B - Surface-enhanced Raman scattering probe and preparation method thereof - Google Patents
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Abstract
The invention relates to a surface-enhanced Raman scattering probe and a preparation method thereof. The probe is an interlayer structure and consists of a core precious-metal nano-rod, an intermediate sandwich layer and a precious-metal shell layer which grows and is formed on the outer surface, wherein a Raman signal molecule is wrapped inside the intermediate sandwich layer. The preparation method comprises the following steps that: the surface of the precious-metal nano-rod absorbs or is coupled with the Raman signal molecule, then the Raman signal molecule is wrapped to form the intermediate sandwich layer through silicon dioxide or polyelectrolyte, and then the precious-metal shell layer grows and is formed outside the intermediate sandwich layer. Through the surface-enhanced Raman scattering probe with the sandwich structure, strong local electromagnetic density is produced through the interaction of the surface plasma between the gold nano-rod and the outer metal shell layer, so the Raman signal is greatly enhanced, the weaknesses that a two-dimensional underlay is difficult to repeat, is expensive and is complicated can be overcome, and at the same time the size of the surface-enhanced Raman scattering probe is smaller than 200nm, biological detection of living bodies and application of biological imaging can be facilitated when the surface-enhanced Raman scattering probe is used as a biological probe.
Description
Technical field
The present invention relates to nanomaterial science, Analytical Chemistry in Life Science field, be specifically related to a kind of Surface enhanced raman spectroscopy (SERS) probe and preparation method thereof.
Background technology
Surface enhanced Raman spectroscopic signals strength ratio normal Raman spectroscopy intensity is high several to tens orders of magnitude, therefore the Surface enhanced raman spectroscopy signal is used to the even monomolecular detection of extremely low concentration, and demonstrates very easy, quick, cheap technical characterstic when detecting organic molecule and biomolecule.From Nie Shuming (science, 1997,275,1102-1106) reported monomolecular Surface enhanced raman spectroscopy (SERS) detection technique in 1997, the Mirkin of Northwestern Univ USA (Science particularly, 2002,297,1536-1540) and Nie Shuming (Nat.Biotech, 2008,26,83-89) group has reported respectively DNA and RNA and in vivo since the SERS detection technique of cancer markers, the research of SERS has received comprising physics, chemistry and biology man's very big concern and caused great research interest.
Thoroughly opening at present the Mysterious Veil that produces the SERS physical mechanism will need the intensive work of people to complete, yet the local Electromagnetic enhancement causes the molecule Raman signal to strengthen to be accepted extensively by people, theoretical calculating single metal particle peripheral electromagnetic field distributes and finds, it is not the enhancing best results of ganoid nano spherical particle, the nano particle that an irregular and end is sharp-pointed on the contrary easily causes strong Raman to strengthen effect, further find that the electromagnetic field between particle can further be enhanced in the molecular aggregation of two or more nanoparticles, the local space of these electromagnetic fields is called as " focus " (hot-spots).In general; the SERS enhancer of single-particle is 106; and the enhancer that " focus " causes can reach tens orders of magnitude; therefore people build nanostructured and two-dimentional SERS substrate (the Nano. Lett. 2006 that can produce " focus " by the whole bag of tricks such as self assembly, micro-processing; 6,2173-2176; Nano. Lett. 2007,7,2080-2088).Yet these methods have the deficiencies such as repeatability is low, complicated operation, preparation costliness.
Summary of the invention
In view of above deficiency, purpose of the present invention is intended to propose a kind of surface-enhanced Raman scattering probe and preparation method thereof, and to solve, product method for making repeatability is low, complicated operation, problem that preparation cost is large, is the development place mat of nanomaterial science, Analytical Chemistry in Life Science.
In order to solve above technical matters, the present invention proposes a kind of surface-enhanced Raman scattering probe, it is characterized in that: described probe is sandwich structure, and the noble metal outer shell that middle sandwich of layers wherein and center sandwich of layers superficial growth form by the noble metal nano of core rod, Raman signal molecule parcel forms.
Further, the noble metal nano of the described core rod gold nanorods between the 500-2000nm wavelength coverage that is length-diameter ratio between 2-6, surface plasma absorption region.
Further, sandwich of layers be thickness 1-10nm silicon dioxide or poly-dielectric in the middle of described, wherein said poly-dielectric is at least a kind of in kayexalate/polypropylene-base amine hydrochlorate, poly propenoic acid propenyl amine hydrochlorate, kayexalate/poly-diallyl dimethyl amine hydrochloride or poly propenoic acid diallyl dimethyl amine hydrochloride.
Further, described Raman signal molecule in the middle of being wrapped in sandwich of layers is at least sulfydryl benzene, sulfydryl puratized agricultural spray, mercaptopyridine, to sulfydryl toluene, Luo Dan name dye molecule, fluorescein isothiocynate, tetramethyl rhodamine-6-isothiocyanic acid, 4-mercaptopyridine, 2, a kind of in 3-dichloro sulfydryl benzene, 2-mono-chlorine sulfydryl benzene or mercaptonaphthalene.
Further, described noble metal outer shell is surperficial continuously smooth and thickness metal shell or the silver metal shell between 10-50nm.
The present invention also proposes a kind of preparation method who prepares above-mentioned surface-enhanced Raman scattering probe, comprises step:
I, pre-prepared length-diameter ratio be the noble metal nano rod between the 500-2000nm wavelength coverage between 2-6, surface plasma absorption region;
II, the noble metal nano rod that the Raman signal molecule is made with the step I reacts, make the Raman signal molecular adsorption or be coupled at the noble metal nano rod of probe surperficial;
III, the noble metal nano rod surface made in the step II form the middle sandwich of layers of parcel Raman signal molecule;
IV, add amination solution in the ethanolic solution disperse system, in the middle of the probe that the step III is made, sandwich of layers finishing amino functional group prepares the precious metal colloid solution of 1-3nm as the growth seed for preparing the noble metal outer shell by the THPC reducing process simultaneously;
V, the probe that will be modified with the amino functional group mix with precious metal colloid solution, make the growth seed of sandwich of layers adsorption noble metal outer shell in the middle of silicon dioxide;
VI, under reductive agent catalysis, the probe that the step V makes is scattered in corresponding precious metal salt solution, the precious metal atom be reduced, along the lattice epitaxial growth of growth seed, forms smooth noble metal outer shell continuously.
Further, described step III adopts the method for ethyl orthosilicate aqueous slkali hydrolysis, the noble metal nano rod surface made in the step II forms the middle sandwich of layers of silicon dioxide of parcel Raman signal molecule, wherein the concentration of ethyl orthosilicate is between 0.1mmol/L-2.0mmol/L, NaOH is regulated aqueous slkali pH value between 6-14, and ethyl orthosilicate is 1:200-200:1 with the mole dosage ratio of noble metal nano rod.
Further, described step III adopts Electrostatic Absorption self-assembly method layer by layer, the noble metal nano rod surface made in the step II forms the middle sandwich of layers of poly-dielectric of parcel Raman signal molecule, for every one deck self assembly, the noble metal nano rod is dissolved in to sodium chloride solution, then adds any poly-dielectric composition, carry out centrifugal treating after 30 minutes, described self assembly is carried out repeatedly for several times, and the poly-dielectric composition that each self assembly adds is identical or different.
Further, in described step IV, amination solution is aminopropyl triethoxysilane or aminopropyl trimethoxysilane.
The proposition of technical solution of the present invention enforcement, compare to prior art and there is outstanding beneficial effect: by the surface-enhanced Raman scattering probe of design sandwich structure, the surface plasma that takes full advantage of gold nanorods and outer metal housing interlayer interacts and produces strong local electromagnetic intensity, greatly strengthen the Raman signal of signaling molecule, this sandwich structure has overcome the repeatability that is difficult to of two-dimensional substrate, the shortcoming of costliness and complicacy, this Surface enhanced raman spectroscopy signal nano-probe size is less than 200 nm simultaneously, be conducive to the biological detection of live body and the application of bio-imaging as bioprobe.
The accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of synthetic sandwich structure.
The ultra-violet absorption spectrum that Fig. 2 is different length-diameter ratio gold nanorods.
Fig. 3 is SiO
2parcel is with the TEM image of Raman signal molecule gold nanorods.
Fig. 4 is that sandwich structure causes the Surface Enhanced Raman Scattering Spectrum to the sulfydryl puratized agricultural spray.
Embodiment
The deficiencies such as creator of the present invention is low for prior art repeatability in the probe preparation, complicated operation, preparation costliness, proposed to innovation a kind of new construction of surface-enhanced Raman scattering probe and completely newly be easy to the method prepared.From this probe of its architectural feature, be sandwich structure, the noble metal outer shell that middle sandwich of layers wherein and center sandwich of layers superficial growth form by the noble metal nano of core rod, Raman signal molecule parcel forms.The noble metal nano of the core rod gold nanorods between the 500-2000nm wavelength coverage that is length-diameter ratio between 2-6, surface plasma absorption region wherein; Silicon dioxide or poly-dielectric that middle sandwich of layers is thickness 1-10nm, the Raman signal molecule wraps up wherein, and outermost noble metal outer shell is surperficial continuously smooth and thickness metal shell or the silver metal shell between 10-50nm.
As preferred version, wherein poly-dielectric is at least a kind of in kayexalate/polypropylene-base amine hydrochlorate, poly propenoic acid propenyl amine hydrochlorate, kayexalate/poly-diallyl dimethyl amine hydrochloride or poly propenoic acid diallyl dimethyl amine hydrochloride.The Raman signal molecule is at least sulfydryl benzene, sulfydryl puratized agricultural spray, mercaptopyridine, to sulfydryl toluene, Luo Dan name dye molecule, fluorescein isothiocynate, tetramethyl rhodamine-6-isothiocyanic acid, 4-mercaptopyridine, 2, a kind of in 3-dichloro sulfydryl benzene, 2-mono-chlorine sulfydryl benzene or mercaptonaphthalene.
Summarize and mainly comprise following six steps from the preparation method of this surface-enhanced Raman scattering probe again: I, pre-prepared length-diameter ratio be the noble metal nano rod between the 500-2000nm wavelength coverage between 2-6, surface plasma absorption region; II, the noble metal nano rod that the Raman signal molecule is made with the step I reacts, make the Raman signal molecular adsorption or be coupled at the noble metal nano rod of probe surperficial; III, the noble metal nano rod surface made in the step II form the middle sandwich of layers of parcel Raman signal molecule; IV, add amination solution in the ethanolic solution disperse system, in the middle of the probe that the step III is made, sandwich of layers finishing amino functional group prepares the precious metal colloid solution of 1-3nm as the growth seed for preparing the noble metal outer shell by the THPC reducing process simultaneously; V, the probe that will be modified with the amino functional group mix with precious metal colloid solution, make the growth seed of sandwich of layers adsorption noble metal outer shell in the middle of silicon dioxide; VI, under reductive agent catalysis, the probe that the step V makes is scattered in corresponding precious metal salt solution, the precious metal atom be reduced, along the lattice epitaxial growth of growth seed, forms smooth noble metal outer shell continuously.
Difference for middle sandwich of layers material, in the step III, the method for this centre sandwich of layers of preparation is also different, can adopt the method for ethyl orthosilicate aqueous slkali hydrolysis, the noble metal nano rod surface made in the step II forms the middle sandwich of layers of silicon dioxide of parcel Raman signal molecule, wherein the concentration of ethyl orthosilicate is between 0.1mmol/L-2.0mmol/L, NaOH is regulated aqueous slkali pH value between 6-14, and ethyl orthosilicate is 1:200-200:1 with the mole dosage ratio of noble metal nano rod.Also can adopt Electrostatic Absorption self-assembly method layer by layer, the noble metal nano rod surface made in the step II forms the middle sandwich of layers of poly-dielectric of parcel Raman signal molecule, for every one deck self assembly, the noble metal nano rod is dissolved in to sodium chloride solution, add again any poly-dielectric composition, carry out centrifugal treating after 30 minutes, described self assembly is carried out repeatedly for several times, and the poly-dielectric composition that each self assembly adds is identical or different.
In addition, in the step IV, amination solution is aminopropyl triethoxysilane or aminopropyl trimethoxysilane.
Below two specific embodiments of preparation method of the present invention are elaborated.This embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
embodiment mono-(middle sandwich of layers is silicon dioxide).
1, pre-prepared (reference literature: Chem.Mater.2003,15.1957) of gold nanorods: the preparation length-diameter ratio is 2-6, the maximal ultraviolet absorption gold nanorods in the 500-2000nm wavelength coverage.
(1) preparation of seed solution: by the HAuCl of the 0.5mmol/L of 5mL
4cetyl trimethyl ammonium bromide (the CTAB of solution and 5mL, 0.2mol/L) solution mixing magnetic agitation, then add 0.6mL newly to join NaBH4(0.01mmol/L) solution, stir 2min under room temperature, discovery has generated filemot gold size solution, as the seed solution of growth gold nanorods.
(2) growth of nanometer gold bar: in the round-bottomed flask of 50mL, add the AgNO of certain volume
3(0.1mol/L) (volume is respectively 0.05mL, 0.08mL, 0.12mL, 0.15mL and 0.18mL to solution, and AgNO
3molal weight determine the major diameter ratio of gold nanorods), then add the CTAB(0.2mol/L of 5mL) HAuCl of solution and 5mL
4(1.0mmol/L) solution, ascorbic acid (0.10mol/L) solution that adds again 50 μ L, after stirring 2min, solution colour is from the faint yellow transparent growth solution that becomes colorless, the seed solution 20 μ L of the gold nanorods growth that finally adds step (1) to obtain, the color of solution occurs significantly to change in 10-20min, shows the formation of gold nanorods.
2, gold nanorods adsorption or coupling Raman signal molecule: the gold nanorods solution that step 1 is made first carries out centrifugal (10000rpm/min twice, 15min), remove supernatant to remove excessive CTAB, the gold nanorods obtained is scattered in to ultrapure water again, the Raman signal molecule of 0.2M (as to the sulfydryl puratized agricultural spray) solution is joined in the gold nanorods aqueous solution, after magnetic agitation 3h, through eccentric cleaning, remove unnecessary Raman signal molecule.
3, gold nanorods surface coated Si O
2thin layer: step 2 being obtained to gold nanorods and disperse in the 20mL aqueous solution, is 10 by 25wt% ammoniacal liquor or NaOH regulator solution pH value, then adds the TEOS(1mM of 4mL) ethanolic solution, magnetic agitation 24h, collect SiO by centrifugal (8000rpm/min, 30min)
2the gold nanorods coated, then water cleans three times and ethanol cleans three times, finally is dispersed in 10mL ethanol with standby.
4, SiO
2the amination on surface is modified: add the nano particle 5mL of step 3 preparation to add 10mL absolute ethyl alcohol and 1mL ammoniacal liquor, add excessive silane coupling agent-aminopropyl triethoxysilane (APTES) or aminopropyl trimethoxysilane (APTMS) after stirring, heated and return and heat up in a steamer 2 hours, by centrifugal collection product (8000rpm/min), through washed with de-ionized water three times and ethanol, clean three times, remove unnecessary silylating reagent, more again be dispersed in the absolute ethyl alcohol of 10mL.
5, the seed solution for preparing the metal shell layer growth: the NaOH(0.2M that adds 1.0mL in the ultrapure water solution of the 48mL) THPC(0.95wt% of solution, the 1mL) HAuCl of aqueous solution and 2.08mL
4(24mM) solution, in 5 seconds, solution, by the colourless brownish black that becomes, is placed on reactant liquor lucifuge refrigeration in the refrigerator of 4 ℃, places more than 2 days with standby.
6, SiO
2the seed of adsorption growing metal outer shell: the nano particle of getting a certain amount of step 4 synthesized adds in the excessive collaurum kind solution of step 5 preparation, gentle agitation is also spent the night, the filtering membrane that is 200nm with aperture filters (or carry out with the centrifugal speed of 4000rpm/min 30min centrifugal treating), obtains SiO
2the seed of adsorption metal shell growth, and be scattered in ultrapure water.
7, the growth of metal shell layer: the K that adds 25mg in the ultrapure water of (1) 100mL
2cO
3hAuCl with 1.5mL
4(24mM) or the AgNO of 0.5mL
3(0.1M) solution, this solution is placed in the refrigerator of 4 ℃ with the refrigeration of lucifuge form, and places more than 2 days standby.
(2) get the 5mL solution that step 6 obtains and join 20mL step 7(1) in solution, after gentle agitation, add fast formaldehyde (37%) aqueous solution of 100 μ l, continue to be stirred to solution colour and become blueness, show the formation of metal nano shell.
embodiment bis-(middle sandwich of layers is poly-dielectric).
The step identical with embodiment mono-no longer repeated at this, only in the difference part, be described in detail as follows: step 3 ', after completing embodiment mono-step 2, the gold nanorods that step 2 is processed is dissolved in the NaCl solution of 1.0mM, add Sodium styrene sulfonate (PSS) to be dissolved in NaCl(1.0mM) stock solution (10mg/ml), centrifugal again after 30 minutes, be scattered in again in the NaCl solution of 1.0mM, add the NaCl(1.0mM that is dissolved in polypropylene-base amine hydrochlorate (PAH)) stock solution (10mg/ml), centrifugal after same 30 minutes, repeatedly several times, form the middle sandwich of layers of polymkeric substance.
4 ', will be through step 3 ' the synthetic gold nano-rod particles gold seeds solution synthetic with embodiment mono-step 5 mixes, and by the physics electrostatic interaction, makes the gold seeds nano particle be adsorbed on polyeletrolyte macromolecule layer surface.
5 ', by step 4 ' nano material processed is scattered in corresponding slaine (HAuCl
4and/or AgNO
3) in solution, reducing action at formaldehyde, metallic ion is reduced to atom, the atom be reduced be take the gold particle of macromolecule surface and is that the crystal seed generation epitaxial growth of growth forms continuous and smooth metal shell, Au/ high molecular polymer/Au(Ag that acquisition has sandwich structure) nano-probe.
Innovative point of the present invention is: (1) Raman signal molecule is between gold nanorods core and metal shell layer, the local " focus " that builds Electromagnetic enhancement by gold nanorods and outer shell metallic surface Plasma Interaction in the single-particle system (hot-spots), reach the purpose that the sequential 2 D substrate produces " focus ", and realize the purpose of the Raman scattering signal enhancing of signaling molecule simultaneously; (2) the nano-probe repeatability of the Surface enhanced raman spectroscopy signal of this sandwich structure is strong, simple to operate, price is cheap and high-sensitive Surface enhanced raman spectroscopy signal, the nanometer Raman microprobe with superior optical characteristics.
Above-mentioned a plurality of embodiment is intended to be convenient to understand technical characterictic of the present invention.So that those skilled in the art can know the innovation essence of grasping technical solution of the present invention, the embodiment limited is not only proposed on function or properties of product.So in addition to the implementation, the present invention can also have other polynary embodiment.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (1)
1. the preparation method of a surface-enhanced Raman scattering probe, is characterized in that, the method comprises following steps:
(1) gold nanorods is pre-prepared, and the preparation length-diameter ratio is 2-6, the maximal ultraviolet absorption gold nanorods in the 500-2000nm wavelength coverage, comprising:
The preparation of a, seed solution: by the HAuCl of the 0.5mmol/L of 5mL
4the cetyl trimethyl ammonium bromide solution that solution is 0.2mol/L with 5mL concentration mixes and magnetic agitation, then add the NaBH4 solution that concentration that 0.6mL newly joins is 0.01mmol/L, stir 2min under room temperature, discovery has generated filemot gold size solution, as the seed solution of growth gold nanorods;
The growth of b, nanometer gold bar: in the round-bottomed flask of 50mL, add volume to be respectively AgNO 0.05mL, 0.08mL, 0.12mL, 0.15mL and 0.18mL, that concentration is 0.1mol/L
3solution, then add the HAuCl that cetyl trimethyl ammonium bromide solution that 5mL concentration is 0.2mol/L and 5mL concentration are 1.0mmol/L
4solution, add again the ascorbic acid solution that 50 μ L concentration are 0.10mol/L, after stirring 2min, solution colour is from the faint yellow transparent growth solution that becomes colorless, the seed solution 20 μ L of the gold nanorods growth that finally adds step a to obtain, the color of solution occurs significantly to change in 10-20min, shows the formation of gold nanorods;
(2) gold nanorods adsorption or coupling Raman signal molecule: the gold nanorods solution that step (1) is made first carry out twice centrifugal, centrifugal rotational speed is 10000rpm/min, time is 15min, remove supernatant to remove excessive cetyl trimethyl ammonium bromide, the gold nanorods obtained is scattered in to ultrapure water again, the Raman signal molecular solution of 0.2M is joined in the gold nanorods aqueous solution, after magnetic agitation 3h, through eccentric cleaning, remove unnecessary Raman signal molecule;
(3) gold nanorods of step (2) being processed is dissolved in the NaCl solution of 1.0mM, add the stock solution containing 10mg/ml Sodium styrene sulfonate, 1.0mM NaCl, centrifugal again after 30 minutes, in the NaCl solution that to be scattered in concentration be 1.0mM again, add the stock solution containing 10mg/ml polypropylene-base amine hydrochlorate, 1.0mM NaCl, centrifugal after same 30 minutes, repeatedly several times, form the middle sandwich of layers of polymkeric substance;
(4) prepare the seed solution of metal shell layer growth: the HAuCl that the THPC aqueous solution that the NaOH solution that the concentration that adds 1.0mL in the ultrapure water solution of 48mL is 0.2M, 1mL concentration are 0.95wt% and 2.08mL concentration are 24mM
4solution, in 5 seconds, solution, by the colourless brownish black that becomes, is placed on reactant liquor lucifuge refrigeration in the refrigerator of 4 ℃, places more than 2 days standby;
(5) gold nano-rod particles that will be synthetic through step (3) the gold seeds solution synthetic with step (4) mixes, and by the physics electrostatic interaction, makes the gold seeds nano particle be adsorbed on polyeletrolyte macromolecule layer surface;
(6) nano material of step (5) being processed is scattered in HAuCl
4and/or AgNO
3in solution, reducing action at formaldehyde, metallic ion is reduced to atom, and the atom be reduced be take the gold particle of macromolecule surface and is that the crystal seed generation epitaxial growth of growth forms continuous and smooth metal shell, Au/ high molecular polymer/Au(Ag that acquisition has sandwich structure) nano-probe.
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| CN101216429A (en) * | 2008-01-07 | 2008-07-09 | 首都师范大学 | SERS biological probe and method for making same |
| CN101694467A (en) * | 2009-10-16 | 2010-04-14 | 东南大学 | Preparation method of surface-enhanced Raman scattering probe |
| CN102346148A (en) * | 2011-08-18 | 2012-02-08 | 江南大学 | Method for detecting surface enhanced Raman scattering of cancer cells based on self-assembled material |
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