CN109813697A - The spacial hot spots Raman spectrum method for detecting surface reinforcement of liquid regulation nano gap - Google Patents
The spacial hot spots Raman spectrum method for detecting surface reinforcement of liquid regulation nano gap Download PDFInfo
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- CN109813697A CN109813697A CN201811634165.9A CN201811634165A CN109813697A CN 109813697 A CN109813697 A CN 109813697A CN 201811634165 A CN201811634165 A CN 201811634165A CN 109813697 A CN109813697 A CN 109813697A
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Abstract
In the Surface enhanced Raman spectroscopy detection process of the prior art, it tends to be difficult to form effective three-dimensional space hot spot, cause the stability of signal and sensitivity to be difficult to be guaranteed, reliability is bad.The present invention relates to analyzing detecting methods, more particularly to a kind of Raman spectrum method for detecting surface reinforcement, disclose a kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, the following steps are included: the liquid that hardly possible is volatilized and molecular scattering section is small is mixed with the metal nanoparticle colloidal sol containing object to be measured molecule, Raman spectrum detection is then carried out.The present invention constructs the spacial hot spots of long-time high stable, improves the stability, repeatability and sensitivity of detection by carrying out liquid regulation to metal nanoparticle colloidal sol.
Description
Technical field
The present invention relates to technical field of analysis and detection more particularly to a kind of spacial hot spots based on liquid regulation nano gap
Raman spectrum method for detecting surface reinforcement.
Background technique
The stability and Code's Sensitivity of Surface enhanced Raman spectroscopy (SERS) signal are the hot spots of current scientific circles' concern
And difficult point, designing and producing the SERS substrate with maximum enhancing becomes the main research interest in the field.Generally speaking, hot
(Bottom-up) from bottom to top and from top to bottom (Top-down) two kinds of nanometer Manufacturing Strategies are usually used in the generation of point, are passed through
Both strategies construct two dimension or three-dimensional hot spot.
Nevertheless, SERS substrate is there is also obvious drawback, i.e. the SERS substrate structure that places one's entire reliance upon nano material,
It include: the relative position of noble metal granule, the size of particle, the spacing of particle, pattern of particle itself etc..While more hot spots
The development of the SERS substrate of three-D space structure, all using method associated with from top to bottom and from bottom to top, it is time-consuming bothersome, need
Want a variety of instrument and equipments.It is in this way, the method for more hot spot SERS substrates is stablized in control synthesis and immature, control synthesis tool
Having the space nanostructure of specific morphology still has biggish randomness.Even if partial 3-D nanostructure SERS substrate has phase
The space structure answered, but still without the three-dimensional space hot spot for being formed with effect.
Existing SERS detection mode is broadly divided into two kinds: first is that dry method, i.e., determinand being added dropwise in substrate, or by substrate
It takes out and dries after being soaked for a period of time, then detected, the feature of this method maximum is that sensitivity is higher, but unstable, can
It is bad by property, first is that being on the other hand easy to produce photochemical reaction, base in the detection process due to the inhomogeneities of substrate itself
Copy for the record or for reproduction body is easy inactivation；Another kind is wet process, i.e., mixes Nano sol and determinand, detected in hygrometric state, by
In not becoming hot spot, sensitivity is low, is difficult to realize and stablizes trace detection.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of spaces based on liquid regulation nano gap
Hot spot Raman spectrum method for detecting surface reinforcement, by constructing long-time high stable spacial hot spots, to realize that surface enhanced is drawn
Stability, repeatability and the sensitivity of graceful spectral detection, and it is simple and easy.
A kind of spacial hot spots Surface enhanced Raman spectroscopy detection side based on liquid regulation nano gap proposed by the present invention
Method, comprising the following steps: by the difficult liquid and the metallic nanoparticle containing object to be measured molecule to volatilize and molecular scattering section is small
Sub- colloidal sol mixing, then carries out Raman spectrum detection.
Preferably, the liquid and the metal nanoparticle containing object to be measured molecule that hardly possible is volatilized and molecular scattering section is small are molten
The volume ratio of glue is 1-5:1.
Preferably, the mass fraction for the liquid that hardly possible is volatilized and molecular scattering section is small is 10-60%.
Preferably, the liquid that hardly possible is volatilized and molecular scattering section is small is at least one of glycerine, ethylene glycol, polyurethane.
Preferably, metal nanoparticle is gold nanoparticle, Nano silver grain or copper nano-particle.
Preferably, the liquid and the metal nanoparticle containing object to be measured molecule that hardly possible is volatilized and molecular scattering section is small are molten
Temperature when glue mixes is room temperature.
Preferably, in Raman spectrum detection process, excitation light wave a length of 532nm, 633nm or 785nm.
The present invention is in the volatilization process of metal nanoparticle colloidal sol, and by being added, some hardly possiblies are volatilized and scattering section is small
Liquid is realized and is regulated and controled to the liquid of metal nanoparticle, its rate of volatilization, the randomness and nanoparticle of nanoparticle movement are slowed down
The certainty of the gap shrinks of son causes long-time high stable spacial hot spots to be formed jointly, thus using spacial hot spots effect, knot
Object to be measured molecule is closed in the free movement of the system hot spot region, to guarantee stability, repeatability and the sensitivity of detection.
The invention proposes the designs of long-time high stable spacial hot spots, in the volatilization process of solvent, be added difficult volatilization and
The small liquid of scattering section, sol volume reduce, and the gap of nanoparticle gradually becomes smaller, and spacial hot spots gradually form, and towards
More efficient hot spot develops and is kept for a period of time.In the unordered middle orderly hot spot of regulation, it is expected to solve current SERS detection process
The problem of middle high stability, high reproducibility and ultrasensitiveness cannot be taken into account.
Detailed description of the invention
Fig. 1 is that silver nano-grain and object to be measured molecule nodularins molecular mixing detect SERS spectrogram in embodiment 1.
Fig. 2 is glycerine and the nano silver particles colloidal sol grade ratio containing object to be measured molecule nodularins in embodiment 1
Example hybrid detection SERS spectrogram.
Fig. 3 is that silver nano-grain and object to be measured molecule nodularins molecular mixing detect 1000cm in embodiment 1-1It is special
Levy SERS time mapping spectrogram at peak.
Fig. 4 is glycerine and the nano silver particles colloidal sol grade ratio containing object to be measured molecule nodularins in embodiment 1
Example hybrid detection 1000cm-1SERS time mapping spectrogram at characteristic peak.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the glycerine that mass fraction is 10% is mixed with the nano silver particles colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 1:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 532nm excitation wavelength
It is detected with Raman spectrometer, as shown in Figs 1-4, wherein Fig. 1 is silver nano-grain and object to be measured molecule nodularins
Molecular mixing detects SERS spectrogram, and Fig. 2 is glycerine and the nano silver particles colloidal sol containing object to be measured molecule nodularins
Equal proportion hybrid detection SERS spectrogram, Fig. 3 are that silver nano-grain and object to be measured molecule nodularins molecular mixing detect
1000cm-1SERS time mapping spectrogram at characteristic peak, Fig. 4 are glycerine and contain object to be measured molecule nodularins
Nano silver particles colloidal sol equal proportion hybrid detection 1000cm-1SERS time mapping spectrogram at characteristic peak.
It is compared from Fig. 1 and Fig. 2: after realizing the liquid regulation to nano-silver ionic using glycerine, forming space
Hot spot-effect detects same concentration nodularins under the same terms, and detection signal improves three times, guarantees detection
Sensitivity.
It is compared from Fig. 3 and Fig. 4: realizing to regulate and control the liquid of nano silver particles using glycerine, slow down its volatilization speed
Rate forms the spacial hot spots of long-time high stable, thus using spacial hot spots effect, in conjunction with nodularins molecule in the system
The free movement of hot spot region, to guarantee stability, repeatability and the sensitivity of detection.
Embodiment 2
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the ethylene glycol that mass fraction is 10% is mixed with the nano silver particles colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 1:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 532nm excitation wavelength
It is detected with Raman spectrometer.
Embodiment 3
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the polyurethane that mass fraction is 20% is mixed with the nano silver particles colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 1:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 532nm excitation wavelength
It is detected with Raman spectrometer.
Embodiment 4
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the polyurethane that mass fraction is 60% is mixed with the nano silver particles colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 5:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 532nm excitation wavelength
It is detected with Raman spectrometer.
Embodiment 5
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the glycerine that mass fraction is 40% is mixed with the gold nanoparticle colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 3:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 633nm excitation wavelength
It is detected with Raman spectrometer.
Embodiment 6
A kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, specific steps are such as
Under: the glycerine that mass fraction is 30% is mixed with the copper nano-particle colloidal sol containing object to be measured molecule nodularins and is pressed
Volume ratio is that 2:1 mixed at room temperature obtains mixed solution, takes 2 μ L mixed solutions drop on silicon wafer, sharp under 785nm excitation wavelength
It is detected with Raman spectrometer.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of spacial hot spots Raman spectrum method for detecting surface reinforcement based on liquid regulation nano gap, which is characterized in that
The following steps are included: the liquid and the metal nanoparticle containing object to be measured molecule that hardly possible is volatilized and molecular scattering section is small is molten
Glue mixing, then carries out Raman spectrum detection.
2. the spacial hot spots Surface enhanced Raman spectroscopy detection side according to claim 1 based on liquid regulation nano gap
Method, which is characterized in that the liquid and the metal nanoparticle containing object to be measured molecule that hardly possible is volatilized and molecular scattering section is small are molten
The volume ratio of glue is 1-5:1.
3. the spacial hot spots Surface enhanced Raman spectroscopy detection according to claim 1 or claim 2 based on liquid regulation nano gap
Method, which is characterized in that the mass fraction for the liquid that hardly possible is volatilized and molecular scattering section is small is 10-60%.
4. the spacial hot spots Surface enhanced Raman spectroscopy based on liquid regulation nano gap described in -3 any one according to claim 1
Detection method, which is characterized in that hardly possible volatilization and the small liquid in molecular scattering section be glycerine, ethylene glycol, in polyurethane at least
It is a kind of.
5. the spacial hot spots Surface enhanced Raman spectroscopy based on liquid regulation nano gap described in -4 any one according to claim 1
Detection method, which is characterized in that metal nanoparticle is gold nanoparticle, Nano silver grain or copper nano-particle.
6. the spacial hot spots Surface enhanced Raman spectroscopy based on liquid regulation nano gap described in -5 any one according to claim 1
Detection method, which is characterized in that the liquid and the metal nano containing object to be measured molecule that hardly possible is volatilized and molecular scattering section is small
Temperature when colloidal sol mixes is room temperature.
7. the spacial hot spots Surface enhanced Raman spectroscopy based on liquid regulation nano gap described in -6 any one according to claim 1
Detection method, which is characterized in that in Raman spectrum detection process, excitation light wave a length of 532nm, 633nm or 785nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113945554A (en) * | 2021-10-15 | 2022-01-18 | 中国科学院合肥物质科学研究院 | SERS detection method of antitumor drug 5-FU in serum |
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| JP2005233637A (en) * | 2004-02-17 | 2005-09-02 | Japan Science & Technology Agency | Raman spectroscopic analysis by gold nanorod thin film |
| US20070153267A1 (en) * | 2005-12-19 | 2007-07-05 | Hong Wang | Arrays of Nano Structures for Surface-Enhanced Raman Scattering |
| CN102181891A (en) * | 2011-04-08 | 2011-09-14 | 温州大学 | Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof |
| CN104897640A (en) * | 2015-05-12 | 2015-09-09 | 吉林大学 | Method used for preparing surface enhanced Raman scattering substrates by adding bearing platforms onto hot spot regions |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005233637A (en) * | 2004-02-17 | 2005-09-02 | Japan Science & Technology Agency | Raman spectroscopic analysis by gold nanorod thin film |
| US20070153267A1 (en) * | 2005-12-19 | 2007-07-05 | Hong Wang | Arrays of Nano Structures for Surface-Enhanced Raman Scattering |
| CN102181891A (en) * | 2011-04-08 | 2011-09-14 | 温州大学 | Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof |
| CN104897640A (en) * | 2015-05-12 | 2015-09-09 | 吉林大学 | Method used for preparing surface enhanced Raman scattering substrates by adding bearing platforms onto hot spot regions |
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| LIANGBAO YANG等: "Metastable state nanoparticle-enhanced Raman spectroscopy for highly sensitive detection", 《CHEMCOMM》 * |
| LIANGBAO YANG等: "Solvent-induced hot spot switch on silver nanorod enhanced Raman spectroscopy", 《ANALYST》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113945554A (en) * | 2021-10-15 | 2022-01-18 | 中国科学院合肥物质科学研究院 | SERS detection method of antitumor drug 5-FU in serum |
| CN113945554B (en) * | 2021-10-15 | 2023-08-18 | 中国科学院合肥物质科学研究院 | SERS detection method for antitumor drug 5-FU in serum |
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