CN102590176A - Surface-enhanced Raman scattering probe and preparation method thereof - Google Patents
Surface-enhanced Raman scattering probe and preparation method thereof Download PDFInfo
- Publication number
- CN102590176A CN102590176A CN201210050801XA CN201210050801A CN102590176A CN 102590176 A CN102590176 A CN 102590176A CN 201210050801X A CN201210050801X A CN 201210050801XA CN 201210050801 A CN201210050801 A CN 201210050801A CN 102590176 A CN102590176 A CN 102590176A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- probe
- sandwich
- raman scattering
- enhanced raman
- 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
Images
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 SERS (SERS) probe and preparation method thereof.
Background technology
Surface enhanced Raman spectroscopic signals strength ratio normal raman spectroscopy intensity is high several to tens one magnitude; Therefore the SERS signal is used to extremely low concentration even monomolecular detection, and when detecting organic molecule and biomolecule, demonstrates very easy, quick, cheap technical characterstic.From Nie Shuming (science, 1997,275; 1102-1106) monomolecular SERS (SERS) detection technique, the particularly Mirkin of Northwestern Univ USA (Science, 2002 have been reported in 1997; 297; 1536-1540) and Nie Shuming (Nat.Biotech, 2008,26; 83-89) group has reported DNA and RNA respectively and in vivo since the SERS detection technique of cancer markers, the research of SERS has received the very big concern that comprises physics, chemistry and biology man 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 accomplish; Yet the enhancing of local electromagnetic field causes the molecule Raman signal to strengthen to be accepted extensively by people; Theoretical Calculation single metal particle peripheral electromagnetic field distributes and finds; The reinforced effects that is not ganoid nano spherical particle is best; Irregular on the contrary and nano particle that an end is sharp-pointed is prone to cause strong Raman reinforced effects, further finds can further be enhanced by the electromagnetic field between the particle in the molecular aggregation of two or more nanoparticles, and 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 one magnitude; Therefore people make up nanostructured and two-dimentional SERS substrate (Nano. Lett. 2006,6, the 2173-2176 that can produce " focus " through the whole bag of tricks such as self assembly, little processing; Nano. Lett. 2007,7,2080-2088).Yet these methods have deficiencies such as repeatability is low, complicated operation, preparation costliness.
Summary of the invention
In view of above deficiency, the object of the invention is intended to propose a kind of surface-enhanced Raman scattering probe and preparation method thereof, and product method for making repeatability is low to solve, complicated operation, problem that preparation cost is big, 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: said probe is a sandwich structure, and the noble metal outer shell that is formed by middle sandwich of layers and the center sandwich of layers superficial growth wherein of the noble metal nano of core rod, Raman signal molecule parcel constitutes.
Further, the noble metal nano of said core rod is a length-diameter ratio between 2-6, the surface plasma absorption region gold nanorods between the 500-2000nm wavelength coverage.
Further; Sandwich of layers is the silicon dioxide of thickness 1-10nm or gathers dielectric in the middle of said, and the wherein said dielectric that gathers is at least a kind of in diallyl dimethyl amine hydrochloride or the poly propenoic acid diallyl dimethyl amine hydrochloride of kayexalate/polypropylene-base amine hydrochlorate, poly propenoic acid propenyl amine hydrochlorate, kayexalate/gather.
Further; Said Raman signal molecule in the middle of being wrapped in the 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-one chlorine sulfydryl benzene or the mercaptonaphthalene.
Further, said 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 are between 2-6, the surface plasma absorption region noble metal nano rod between the 500-2000nm wavelength coverage;
II, with the noble metal nano rod reaction that Raman signal molecule and step I make, make the Raman signal molecular adsorption or be coupled at the noble metal nano rod surface of probe;
III, the noble metal nano rod surface that makes in the step II form the middle sandwich of layers of parcel Raman signal molecule;
IV, in the ethanolic solution disperse system, add amination solution; The middle sandwich laminar surface of probe to the step III makes is modified the amino functional group, prepares the growth seed of the precious metal colloid solution of 1-3nm as preparation noble metal outer shell with 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 laminar surface absorption noble metal outer shell in the middle of the silicon dioxide;
VI, under reductive agent catalysis, the probe that the step V makes is scattered in the corresponding precious metal salt solution, the precious metal atom that is reduced forms smooth noble metal outer shell continuously along the lattice epitaxial growth of growth seed.
Further; Said step III adopts the method for ethyl orthosilicate aqueous slkali hydrolysis; Form the middle sandwich of layers of silicon dioxide of parcel Raman signal molecule on the noble metal nano rod surface that the step II makes; Wherein the concentration of ethyl orthosilicate is between 0.1mmol/L-2.0mmol/L, and 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, said step III adopts Electrostatic Absorption self-assembly method layer by layer, forms the sandwich of layers in the middle of the dielectric of gathering of parcel Raman signal molecule on the noble metal nano rod surface that the step II makes; For each layer self assembly; The noble metal nano rod is dissolved in sodium chloride solution, adds any again and gather dielectric composition, carry out centrifugal treating after 30 minutes; Said self assembly is carried out for several times repeatedly, and each time self assembly is added, and to gather dielectric composition identical or different.
Further, amination solution is aminopropyl triethoxysilane or aminopropyl trimethoxysilane in the said step IV.
The proposition of technical scheme of the present invention and enforcement; Compare to prior art and have outstanding beneficial effect: through the surface-enhanced Raman scattering probe of design sandwich structure; The surface plasma that makes full use of gold nanorods and outer metal housing interlayer interacts and produces strong local electromagnetic intensity; The Raman signal of very big enhancing signal molecule; This sandwich structure has overcome the shortcoming that is difficult to repeatability, costliness and complicacy of two-dimensional substrate, and this SERS signal nano-probe size helps the biological detection of live body and the application of bio-imaging less than 200 nm as bioprobe simultaneously.
Description of drawings
Fig. 1 is the synthetic route synoptic diagram of synthetic sandwich structure.
Fig. 2 is the ultra-violet absorption spectrum of different length-diameter ratio gold nanorods.
Fig. 3 is SiO
2Parcel is with the TEM image of Raman signal molecule gold nanorods.
Fig. 4 causes the SERS spectrum to the sulfydryl puratized agricultural spray for sandwich structure.
Embodiment
Deficiencies such as creator of the present invention is low to prior art repeatability in the probe preparation, complicated operation, preparation costliness have proposed to innovation a kind of new construction of surface-enhanced Raman scattering probe and the method that completely newly is easy to prepare thereof.From this probe of its architectural feature is sandwich structure, and the noble metal outer shell that is formed by middle sandwich of layers and the center sandwich of layers superficial growth wherein of the noble metal nano of core rod, Raman signal molecule parcel constitutes.Wherein the noble metal nano of core rod is a length-diameter ratio between 2-6, the surface plasma absorption region gold nanorods between the 500-2000nm wavelength coverage; Middle sandwich of layers is the silicon dioxide of thickness 1-10nm or gathers dielectric, and 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 gather dielectric and be at least a kind of in diallyl dimethyl amine hydrochloride or the poly propenoic acid diallyl dimethyl amine hydrochloride of kayexalate/polypropylene-base amine hydrochlorate, poly propenoic acid propenyl amine hydrochlorate, kayexalate/gather.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-one chlorine sulfydryl benzene or the mercaptonaphthalene.
Summarize from the preparation method of this surface-enhanced Raman scattering probe and mainly comprise following six steps: I, pre-prepared length-diameter ratio are between 2-6, the surface plasma absorption region noble metal nano rod between the 500-2000nm wavelength coverage; II, with the noble metal nano rod reaction that Raman signal molecule and step I make, make the Raman signal molecular adsorption or be coupled at the noble metal nano rod surface of probe; III, the noble metal nano rod surface that makes in the step II form the middle sandwich of layers of parcel Raman signal molecule; IV, in the ethanolic solution disperse system, add amination solution; The middle sandwich laminar surface of probe to the step III makes is modified the amino functional group, prepares the growth seed of the precious metal colloid solution of 1-3nm as preparation noble metal outer shell with 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 laminar surface absorption noble metal outer shell in the middle of the silicon dioxide; VI, under reductive agent catalysis, the probe that the step V makes is scattered in the corresponding precious metal salt solution, the precious metal atom that is reduced forms smooth noble metal outer shell continuously along the lattice epitaxial growth of growth seed.
Difference to middle sandwich of layers material; The method of this centre sandwich of layers of preparation is also different in the step III; Can adopt the method for ethyl orthosilicate aqueous slkali hydrolysis, form the middle sandwich of layers of silicon dioxide of parcel Raman signal molecule on the noble metal nano rod surface that the step II makes, 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 that makes in the step II forms the sandwich of layers in the middle of the dielectric of gathering of parcel Raman signal molecule, for each layer self assembly, the noble metal nano rod is dissolved in sodium chloride solution; Add any again and gather dielectric composition; Carry out centrifugal treating after 30 minutes, said self assembly is carried out for several times repeatedly, and each time self assembly is added, and to gather dielectric composition identical or different.
In addition, amination solution is aminopropyl triethoxysilane or aminopropyl trimethoxysilane in the step IV.
Below two specific embodiments of preparation method of the present invention are elaborated.This embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
embodiment one (middle sandwich of layers is a silicon dioxide).
1, the pre-prepared of gold nanorods (reference literature: Chem.Mater.2003,15.1957): 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: with the HAuCl of the 0.5mmol/L of 5mL
4Cetyl trimethyl ammonium bromide (the CTAB of solution and 5mL; 0.2mol/L) solution mixing and magnetic agitation, add 0.6mL then and newly join NaBH4 (0.01mmol/L) solution, stir 2min under the room temperature; Discovery has generated filemot gold size solution, as the seed solution of growth gold nanorods.
(2) growth of nm of gold rod: 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
3The major diameter ratio of molal weight decision gold nanorods), add CTAB (0.2mol/L) solution of 5mL and the HAuCl of 5mL then
4(1.0mmol/L) solution; Ascorbic acid (0.10mol/L) solution that adds 50 μ L again; Solution colour is from the faint yellow transparent growth solution that becomes colorless after stirring 2min; Add the seed solution 20 μ L of the gold nanorods growth that step (1) obtains at last, obvious variation takes place in the color of solution in 10-20min, show the formation of gold nanorods.
2, gold nanorods surface adsorption or coupling Raman signal molecule: the gold nanorods solution that step 1 is made carries out two times centrifugal (10000rpm/min earlier; 15min); Remove supernatant to remove excessive CTAB, the gold nanorods that obtains is scattered in ultrapure water again, Raman signal molecule (as to the sulfydryl puratized agricultural spray) solution of 0.2M is joined in the gold nanorods WS; Behind the magnetic agitation 3h, remove unnecessary Raman signal molecule through eccentric cleaning.
3, gold nanorods surface coated Si O
2Thin layer: step 2 is obtained gold nanorods disperse in the 20mL WS, using 25wt% ammoniacal liquor or NaOH regulator solution pH value is 10, adds TEOS (1mM) ethanolic solution of 4mL then, and magnetic agitation 24h is through centrifugal (8000rpm/min, 30min) collection SiO
2The gold nanorods that coats, water cleaning three times and ethanol clean three times again, are dispersed at last in the 10mL ethanol with subsequent use.
4, SiO
2The amination on surface is modified: the nano particle 5mL that adds step 3 preparation adds 10mL absolute ethyl alcohol and 1mL ammoniacal liquor; Excessive silane coupling agent-aminopropyl triethoxysilane (APTES) or the aminopropyl trimethoxysilane (APTMS) of back adding stirs; Heat and return and heated up in a steamer 2 hours,, clean three times through washed with de-ionized water three times and ethanol through centrifugal collection product (8000rpm/min); Remove unnecessary silylating reagent, be dispersed in again in the absolute ethyl alcohol of 10mL again.
5, the seed solution of preparation metal shell layer growth: NaOH (0.2M) solution, THPC (0.95wt%) WS of 1mL and the HAuCl of 2.08mL that in the ultrapure water solution of 48mL, add 1.0mL
4(24mM) solution, solution is placed on reactant liquor lucifuge refrigeration in 4 ℃ the refrigerator by the colourless brownish black that becomes in 5 seconds, places more than 2 days with subsequent use.
6, SiO
2The seed of surface adsorption growing metal outer shell: get the nano particle that a certain amount of step 4 synthesizes and add in the excessive collaurum kind solution of step 5 preparation; Gentle agitation is also spent the night; Use the filtering membrane filtration (perhaps with the centrifugal speed of 4000rpm/min carry out the centrifugal treating of 30min) of aperture, obtain SiO as 200nm
2The seed of surface adsorption metal shell growth, and be scattered in the 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 are placed in 4 ℃ the refrigerator with the refrigeration of lucifuge form, and place more than 2 days subsequent use.
(2) get the 5mL solution that step 6 obtains and join in 20mL step 7 (1) solution, after the gentle agitation, add formaldehyde (37%) WS of 100 μ l fast, continue to be stirred to solution colour and become blueness, show the formation of metal nano shell.
embodiment two (middle sandwich of layers is for gathering dielectric).
No longer repeat at this with embodiment one identical step; Only introduce as follows in detail: step 3 in the difference part ', accomplish after embodiment one step 2, the gold nanorods that step 2 is handled is dissolved in the NaCl solution of 1.0mM, adding SSS (PSS) is dissolved in the stock solution (10mg/ml) of NaCl (1.0mM); Centrifugal again after 30 minutes; Be scattered in again in the NaCl solution of 1.0mM, add the stock solution (10mg/ml) of the NaCl (1.0mM) that is dissolved in polypropylene-base amine hydrochlorate (PAH), centrifugal after same 30 minutes; Repeatedly several times, form the middle sandwich of layers of polymkeric substance.
4 ', will be through step 3 ' synthetic gold nano-rod particles mixes with the synthetic gold seeds solution of embodiment one step 5, and it is surperficial to make the gold seeds nano particle be adsorbed on the polyeletrolyte macromolecule layer through the physics electrostatic interaction.
5 ', with step 4 ' nano material handled is scattered in corresponding metal salt (HAuCl
4And/or AgNO
3) in the solution; Reducing action at formaldehyde; Metallic ion is reduced to atom; The atom that is reduced is that the crystal seed generation epitaxial growth of growth forms continuous and smooth metal shell with the gold particle of macromolecule surface, obtains Au/ high molecular polymer/Au (Ag) nano-probe with sandwich structure.
Innovative point of the present invention is: (1) Raman signal molecule is between gold nanorods core and the metal shell layer; In the single-particle system, make up local " focus " that electromagnetic field strengthens (hot-spots) through gold nanorods and outer shell metallic surface plasma interaction; 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 SERS signal of this sandwich structure is strong, simple to operate, price is cheap and high-sensitive SERS 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 scheme of the present invention, be not the embodiment that only on function or properties of product, proposes qualification.So except that the foregoing description, 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 (9)
1. surface-enhanced Raman scattering probe, it is characterized in that: said probe is a sandwich structure, the noble metal outer shell that is formed by middle sandwich of layers and the center sandwich of layers superficial growth wherein of the noble metal nano rod of core, Raman signal molecule parcel constitutes.
2. a kind of surface-enhanced Raman scattering probe as claimed in claim 1 is characterized in that: the noble metal nano of said core rod for length-diameter ratio between 2-6, surface plasma absorption region gold nanorods between the 500-2000nm wavelength coverage.
3. a kind of surface-enhanced Raman scattering probe as claimed in claim 1; It is characterized in that: sandwich of layers is the silicon dioxide of thickness 1-10nm or gathers dielectric in the middle of said, and the wherein said dielectric that gathers is at least a kind of in diallyl dimethyl amine hydrochloride or the poly propenoic acid diallyl dimethyl amine hydrochloride of kayexalate/polypropylene-base amine hydrochlorate, poly propenoic acid propenyl amine hydrochlorate, kayexalate/gather.
4. a kind of surface-enhanced Raman scattering probe as claimed in claim 1; It is characterized in that: the said Raman signal molecule in the middle of being wrapped in the 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-one chlorine sulfydryl benzene or the mercaptonaphthalene.
5. a kind of surface-enhanced Raman scattering probe as claimed in claim 1 is characterized in that: said noble metal outer shell is surperficial continuously smooth and thickness metal shell or the silver metal shell between 10-50nm.
6. the preparation method of a surface-enhanced Raman scattering probe is characterized in that comprising step:
I, pre-prepared length-diameter ratio are between 2-6, the surface plasma absorption region noble metal nano rod between the 500-2000nm wavelength coverage;
II, with the noble metal nano rod reaction that Raman signal molecule and step I make, make the Raman signal molecular adsorption or be coupled at the noble metal nano rod surface of probe;
III, the noble metal nano rod surface that makes in the step II form the middle sandwich of layers of parcel Raman signal molecule;
IV, in the ethanolic solution disperse system, add amination solution; The middle sandwich laminar surface of probe to the step III makes is modified the amino functional group, prepares the growth seed of the precious metal colloid solution of 1-3nm as preparation noble metal outer shell with 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 laminar surface absorption noble metal outer shell in the middle of the silicon dioxide;
VI, under reductive agent catalysis, the probe that the step V makes is scattered in the corresponding precious metal salt solution, the precious metal atom that is reduced forms smooth noble metal outer shell continuously along the lattice epitaxial growth of growth seed.
7. the preparation method of a kind of surface-enhanced Raman scattering probe as claimed in claim 6; It is characterized in that: said step III adopts the method for ethyl orthosilicate aqueous slkali hydrolysis; Form the middle sandwich of layers of silicon dioxide of parcel Raman signal molecule on the noble metal nano rod surface that the step II makes; 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.
8. the preparation method of a kind of surface-enhanced Raman scattering probe as claimed in claim 6; It is characterized in that: said step III adopts Electrostatic Absorption self-assembly method layer by layer; The noble metal nano rod surface that makes in the step II forms the sandwich of layers in the middle of the dielectric of gathering of parcel Raman signal molecule, for each layer self assembly, the noble metal nano rod is dissolved in sodium chloride solution; Add any again and gather dielectric composition; Carry out centrifugal treating after 30 minutes, said self assembly is carried out for several times repeatedly, and each time self assembly is added, and to gather dielectric composition identical or different.
9. the preparation method of a kind of surface-enhanced Raman scattering probe as claimed in claim 6, it is characterized in that: amination solution is aminopropyl triethoxysilane or aminopropyl trimethoxysilane in the said step IV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050801.XA CN102590176B (en) | 2012-03-01 | 2012-03-01 | Surface-enhanced Raman scattering probe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050801.XA CN102590176B (en) | 2012-03-01 | 2012-03-01 | Surface-enhanced Raman scattering probe and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102590176A true CN102590176A (en) | 2012-07-18 |
| CN102590176B CN102590176B (en) | 2014-01-01 |
Family
ID=46479116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210050801.XA Expired - Fee Related CN102590176B (en) | 2012-03-01 | 2012-03-01 | Surface-enhanced Raman scattering probe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102590176B (en) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103048306A (en) * | 2012-12-18 | 2013-04-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Core-shell nanogold biological probe with high SERS (surface enhanced Raman scattering) effect and preparation and application thereof |
| CN103830868A (en) * | 2014-03-04 | 2014-06-04 | 福建皓尔宝新材料科技有限公司 | Coating-functionalizing surface finishing agent composition as well as preparation and application thereof |
| CN103862032A (en) * | 2014-02-26 | 2014-06-18 | 国家纳米科学中心 | Core-shell precious metal nanorod with square superlattice and self-assembly method thereof |
| CN103990812A (en) * | 2014-06-06 | 2014-08-20 | 厦门大学 | Method for preparing surface enhanced Raman substrate |
| CN104741604A (en) * | 2015-04-13 | 2015-07-01 | 国家纳米科学中心 | Sea cucumber-like nano composite material and preparation method and application thereof |
| CN104777140A (en) * | 2015-04-14 | 2015-07-15 | 电子科技大学 | Targeted mesoporous molecular imaging probe and preparation method thereof |
| CN104897646A (en) * | 2015-06-26 | 2015-09-09 | 中南大学 | Au@ p-mercapto-phenylmercaptan @Au combination Raman probe and production method thereof |
| CN105110288A (en) * | 2015-08-27 | 2015-12-02 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN105169495A (en) * | 2015-09-18 | 2015-12-23 | 天津市赛宁生物工程技术有限公司 | Preparation method of degradable metal guide wires for breast cancer sound-light imaging diagnosis and treatment |
| WO2016150125A1 (en) * | 2015-03-26 | 2016-09-29 | 厦门大学 | Core-shell structure nanoparticle internally containing internal standard molecules and surface-enhanced raman quantitative detection method |
| CN106179542A (en) * | 2016-07-11 | 2016-12-07 | 上海理工大学 | Porous gold mercury ion detecting Fluorescence chip preparation method and Fluorescence chip purposes |
| CN106645090A (en) * | 2017-01-11 | 2017-05-10 | 华南师范大学 | Novel SERS substrate-based method for quantitatively testing pathogenic bacteria |
| CN107043621A (en) * | 2017-06-14 | 2017-08-15 | 江南大学 | A kind of gold nano nested structure composite particles for strengthening fluorescence and preparation method thereof |
| CN107116233A (en) * | 2017-07-03 | 2017-09-01 | 安徽工业大学 | A kind of preparation method of branched ultra-fine Pt nano wires |
| CN107213462A (en) * | 2017-07-25 | 2017-09-29 | 国家纳米科学中心 | Nanogold particle of method and ICG cladding a kind of of enhancing ICG singlet oxygen yield and preparation method thereof |
| CN108627492A (en) * | 2017-03-22 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of pH responsive types surface-enhanced Raman scattering probe and its preparation |
| CN108941608A (en) * | 2018-08-23 | 2018-12-07 | 安徽中科赛飞尔科技有限公司 | A kind of regulatable silver-colored/golden cavity nanometer rods construction method of shell thickness and its application |
| CN109570488A (en) * | 2018-12-18 | 2019-04-05 | 深圳先进技术研究院 | Nano particle and its preparation method and application, medicament |
| WO2019179386A1 (en) * | 2018-03-19 | 2019-09-26 | 上海交通大学 | Raman probe, and manufacturing method and application thereof |
| CN110618123A (en) * | 2019-09-11 | 2019-12-27 | 亳州市新健康科技有限公司 | Efficient surface-enhanced Raman scattering substrate material and preparation method thereof |
| CN110699953A (en) * | 2019-10-10 | 2020-01-17 | 天津工业大学 | Preparation method of nano gold film anti-counterfeiting fabric |
| CN111208113A (en) * | 2020-02-28 | 2020-05-29 | 中国地质大学（北京） | Self-powered SERS substrate based on flexible piezoelectric film loaded with nano Ag and application |
| CN111289493A (en) * | 2020-03-27 | 2020-06-16 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
| CN111363538A (en) * | 2020-04-30 | 2020-07-03 | 东南大学 | Dual-mode optical super-resolution imaging probe and preparation method thereof |
| CN112229828A (en) * | 2020-08-11 | 2021-01-15 | 嘉兴学院 | SERS active substrate for high-selectivity capture of sudan dye and preparation method thereof |
| CN114264805A (en) * | 2021-12-06 | 2022-04-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of SERS enhancement-based probe, product and application thereof |
| CN114486852A (en) * | 2021-04-26 | 2022-05-13 | 上海交通大学 | Method for detecting target molecule |
| CN114685311A (en) * | 2020-12-29 | 2022-07-01 | 华中师范大学 | Azo aromatic compound, application thereof and reagent for enhancing Raman scattering signals |
| CN115032183B (en) * | 2022-04-28 | 2023-06-27 | 苏州大学 | Device and method for measuring colloid stability and collision strength among colloid particles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050130324A1 (en) * | 1998-03-11 | 2005-06-16 | William Marsh Rice University | Metal nanoshells for biosensing applications |
| US20050217424A1 (en) * | 1999-10-06 | 2005-10-06 | Natan Michael J | Surface enhanced spectroscopy-active composite nanoparticles |
| CN101216429A (en) * | 2008-01-07 | 2008-07-09 | 首都师范大学 | SERS biological probe and method for making same |
| US20090258373A1 (en) * | 2008-04-11 | 2009-10-15 | Becton, Dickinson And Company | Methods of controlling the sensitivity and dynamic range of a homogeneous assay |
| 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 |
-
2012
- 2012-03-01 CN CN201210050801.XA patent/CN102590176B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050130324A1 (en) * | 1998-03-11 | 2005-06-16 | William Marsh Rice University | Metal nanoshells for biosensing applications |
| US20050217424A1 (en) * | 1999-10-06 | 2005-10-06 | Natan Michael J | Surface enhanced spectroscopy-active composite nanoparticles |
| CN101216429A (en) * | 2008-01-07 | 2008-07-09 | 首都师范大学 | SERS biological probe and method for making same |
| US20090258373A1 (en) * | 2008-04-11 | 2009-10-15 | Becton, Dickinson And Company | Methods of controlling the sensitivity and dynamic range of a homogeneous assay |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 邹楠: "金纳米棒复合材料的合成及其表面增强拉曼散射研究", 《CNKI中国优秀硕士学位论文全文数据库》, 15 August 2010 (2010-08-15) * |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103048306B (en) * | 2012-12-18 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | There is core-shell nano gold bioprobe and the Synthesis and applications of high SERS effect |
| CN103048306A (en) * | 2012-12-18 | 2013-04-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Core-shell nanogold biological probe with high SERS (surface enhanced Raman scattering) effect and preparation and application thereof |
| CN103862032A (en) * | 2014-02-26 | 2014-06-18 | 国家纳米科学中心 | Core-shell precious metal nanorod with square superlattice and self-assembly method thereof |
| CN103862032B (en) * | 2014-02-26 | 2016-08-03 | 国家纳米科学中心 | The nucleocapsid noble metal nano rod of four directions superlattices and self-assembling method thereof |
| CN103830868B (en) * | 2014-03-04 | 2017-05-24 | 福建皓尔宝新材料科技有限公司 | Coating-functionalizing surface finishing agent composition as well as preparation and application thereof |
| CN103830868A (en) * | 2014-03-04 | 2014-06-04 | 福建皓尔宝新材料科技有限公司 | Coating-functionalizing surface finishing agent composition as well as preparation and application thereof |
| CN103990812A (en) * | 2014-06-06 | 2014-08-20 | 厦门大学 | Method for preparing surface enhanced Raman substrate |
| WO2016150125A1 (en) * | 2015-03-26 | 2016-09-29 | 厦门大学 | Core-shell structure nanoparticle internally containing internal standard molecules and surface-enhanced raman quantitative detection method |
| CN104741604A (en) * | 2015-04-13 | 2015-07-01 | 国家纳米科学中心 | Sea cucumber-like nano composite material and preparation method and application thereof |
| CN104777140A (en) * | 2015-04-14 | 2015-07-15 | 电子科技大学 | Targeted mesoporous molecular imaging probe and preparation method thereof |
| CN104777140B (en) * | 2015-04-14 | 2017-09-15 | 电子科技大学 | One kind targeting mesoporous molecular image probe and preparation method thereof |
| CN104897646A (en) * | 2015-06-26 | 2015-09-09 | 中南大学 | Au@ p-mercapto-phenylmercaptan @Au combination Raman probe and production method thereof |
| CN104897646B (en) * | 2015-06-26 | 2017-07-28 | 中南大学 | A kind of Au@are combined Raman microprobe preparation method to sulfydryl benzenethiol@Au |
| CN105110288B (en) * | 2015-08-27 | 2017-01-25 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN105110288A (en) * | 2015-08-27 | 2015-12-02 | 陕西科技大学 | Method for preparing patterned Ag nano-particles |
| CN105169495A (en) * | 2015-09-18 | 2015-12-23 | 天津市赛宁生物工程技术有限公司 | Preparation method of degradable metal guide wires for breast cancer sound-light imaging diagnosis and treatment |
| CN106179542A (en) * | 2016-07-11 | 2016-12-07 | 上海理工大学 | Porous gold mercury ion detecting Fluorescence chip preparation method and Fluorescence chip purposes |
| CN106645090A (en) * | 2017-01-11 | 2017-05-10 | 华南师范大学 | Novel SERS substrate-based method for quantitatively testing pathogenic bacteria |
| CN108627492A (en) * | 2017-03-22 | 2018-10-09 | 中国科学院烟台海岸带研究所 | A kind of pH responsive types surface-enhanced Raman scattering probe and its preparation |
| CN107043621A (en) * | 2017-06-14 | 2017-08-15 | 江南大学 | A kind of gold nano nested structure composite particles for strengthening fluorescence and preparation method thereof |
| CN107116233B (en) * | 2017-07-03 | 2018-11-30 | 安徽工业大学 | A kind of preparation method of the ultra-fine Pt nano wire of branching |
| CN107116233A (en) * | 2017-07-03 | 2017-09-01 | 安徽工业大学 | A kind of preparation method of branched ultra-fine Pt nano wires |
| CN107213462A (en) * | 2017-07-25 | 2017-09-29 | 国家纳米科学中心 | Nanogold particle of method and ICG cladding a kind of of enhancing ICG singlet oxygen yield and preparation method thereof |
| WO2019179386A1 (en) * | 2018-03-19 | 2019-09-26 | 上海交通大学 | Raman probe, and manufacturing method and application thereof |
| CN108941608A (en) * | 2018-08-23 | 2018-12-07 | 安徽中科赛飞尔科技有限公司 | A kind of regulatable silver-colored/golden cavity nanometer rods construction method of shell thickness and its application |
| CN109570488A (en) * | 2018-12-18 | 2019-04-05 | 深圳先进技术研究院 | Nano particle and its preparation method and application, medicament |
| CN109570488B (en) * | 2018-12-18 | 2021-03-23 | 深圳先进技术研究院 | Nanoparticle, preparation method and application thereof, and medicament |
| CN110618123A (en) * | 2019-09-11 | 2019-12-27 | 亳州市新健康科技有限公司 | Efficient surface-enhanced Raman scattering substrate material and preparation method thereof |
| CN110618123B (en) * | 2019-09-11 | 2022-01-28 | 亳州市新健康科技有限公司 | Efficient surface-enhanced Raman scattering substrate material and preparation method thereof |
| CN110699953B (en) * | 2019-10-10 | 2022-05-31 | 天津工业大学 | Preparation method of nano gold film anti-counterfeiting fabric |
| CN110699953A (en) * | 2019-10-10 | 2020-01-17 | 天津工业大学 | Preparation method of nano gold film anti-counterfeiting fabric |
| CN111208113A (en) * | 2020-02-28 | 2020-05-29 | 中国地质大学（北京） | Self-powered SERS substrate based on flexible piezoelectric film loaded with nano Ag and application |
| CN111208113B (en) * | 2020-02-28 | 2021-06-29 | 中国地质大学（北京） | Self-powered SERS substrate based on flexible piezoelectric film loaded with nano Ag and application |
| CN111289493A (en) * | 2020-03-27 | 2020-06-16 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
| CN111363538A (en) * | 2020-04-30 | 2020-07-03 | 东南大学 | Dual-mode optical super-resolution imaging probe and preparation method thereof |
| CN112229828A (en) * | 2020-08-11 | 2021-01-15 | 嘉兴学院 | SERS active substrate for high-selectivity capture of sudan dye and preparation method thereof |
| CN114685311A (en) * | 2020-12-29 | 2022-07-01 | 华中师范大学 | Azo aromatic compound, application thereof and reagent for enhancing Raman scattering signals |
| CN114486852A (en) * | 2021-04-26 | 2022-05-13 | 上海交通大学 | Method for detecting target molecule |
| CN114264805A (en) * | 2021-12-06 | 2022-04-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of SERS enhancement-based probe, product and application thereof |
| CN115032183B (en) * | 2022-04-28 | 2023-06-27 | 苏州大学 | Device and method for measuring colloid stability and collision strength among colloid particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102590176B (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102590176B (en) | Surface-enhanced Raman scattering probe and preparation method thereof | |
| Lai et al. | Recent progress on graphene-based substrates for surface-enhanced Raman scattering applications | |
| Zhang et al. | Small and sharp triangular silver nanoplates synthesized utilizing tiny triangular nuclei and their excellent SERS activity for selective detection of thiram residue in soil | |
| Lai et al. | A review of the preparation and application of magnetic nanoparticles for surface-enhanced Raman scattering | |
| Kuo et al. | Synthesis of highly faceted pentagonal-and hexagonal-shaped gold nanoparticles with controlled sizes by sodium dodecyl sulfate | |
| Nilghaz et al. | Surface-enhanced Raman spectroscopy substrates for food safety and quality analysis | |
| Liu et al. | Distinctive enhanced and tunable plasmon resonant absorption from controllable Au@ Cu2O nanoparticles: experimental and theoretical modeling | |
| Jena et al. | Synthesis of branched Ag nanoflowers based on a bioinspired technique: their surface enhanced Raman scattering and antibacterial activity | |
| Dasary et al. | Alizarin dye based ultrasensitive plasmonic SERS probe for trace level cadmium detection in drinking water | |
| Sun et al. | Selective decoration of metal nanoparticles inside or outside of organic microstructures via self-assembly of resorcinarene | |
| Tian et al. | SERS-based immunoassay and degradation of CA19-9 mediated by gold nanowires anchored magnetic–semiconductor nanocomposites | |
| Barveen et al. | Photochemical synthesis of Ag/Au/AgCl heterostructure from Ag nanowires as a reusable SERS substrate for ultrasensitive detection of analgesics and antibiotics | |
| CN103286312A (en) | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles | |
| CN101482554B (en) | Magnetic Raman nano composite material used for biological separation and detection, and production method thereof | |
| Kołątaj et al. | Formation of bifunctional conglomerates composed of magnetic γ-Fe2O3 nanoparticles and various noble metal nanostructures | |
| Chen et al. | Highly sensitive determination of dopamine based on the aggregation of small-sized gold nanoparticles | |
| Sadiq et al. | Gold nanoparticles-based colorimetric assays for environmental monitoring and food safety evaluation | |
| Zhou et al. | Recent advances of plasmonic gold nanoparticles in optical sensing and therapy | |
| Dikkumbura et al. | Growth Dynamics of Colloidal Silver–Gold Core–Shell Nanoparticles Studied by In Situ Second Harmonic Generation and Extinction Spectroscopy | |
| CN105842229A (en) | Core-shell SERS (surface enhanced Raman spectroscopy) probe, method for preparing same and application of core-shell SERS probe to trace arsenate ion detection | |
| Jiang et al. | The synthesis of four–layer gold–silver–polymer–silver core–shell nanomushroom with inbuilt Raman molecule for surface–enhanced Raman scattering | |
| Balasubramanian et al. | Facile aqueous phase synthesis of (200) faceted Au-AgCl cubes using bael gum and its activity toward oxidation and detection of o-PDA | |
| CN103487378A (en) | Gold nanorod aggregation based circular dichroism spectrum method for DNA detection | |
| CN104858445A (en) | Controllable assembly method of plasmon polariton baseball 'corn' structure | |
| Sangubotla et al. | Fluorometric biosensor based on boronic acid-functionalized ZnO-derived nanostructures for the detection of N-acetylneuraminic acid and its in vivo bio-imaging studies |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140101 Termination date: 20210301 |