CN106990092B - A kind of preparation method of the highly sensitive portable SERS substrate based on acupuncture acupuncture needle - Google Patents
A kind of preparation method of the highly sensitive portable SERS substrate based on acupuncture acupuncture needle Download PDFInfo
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- CN106990092B CN106990092B CN201710250359.8A CN201710250359A CN106990092B CN 106990092 B CN106990092 B CN 106990092B CN 201710250359 A CN201710250359 A CN 201710250359A CN 106990092 B CN106990092 B CN 106990092B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The preparation method for the highly sensitive portable SERS substrate based on acupuncture acupuncture needle that the invention discloses a kind of comprising following steps: will be spare after the cleaning of acupuncture acupuncture needle;Synthesize the stable gold nano grain of PVP;After PVP stable gold nano grain eccentric cleaning, the gold nano particle colloidal sols of the 10-90% for original content are concentrated;It will be impregnated in acupuncture acupuncture needle insertion gold nano particle colloidal sols after processing;It will be inserted into measuring samples solution after acupuncture acupuncture needle drying after modifying, carry out SERS detection using Portable Raman spectrometer.Sensitivity mainly is improved using the bimetallic coupling of acupuncture needle and gold nano grain, the stability of substrate is improved using the space steric effect of PVP, the reproducibility of substrate is improved using the dense arrangement between gold nano grain.Preparation method is simple, easy to carry, and is suitable in any liquid environment.
Description
Technical field
The invention belongs to the technical fields of chemical component detection, and in particular to a kind of based on the highly sensitive portable of acupuncture acupuncture needle
The preparation method of formula SERS substrate.
Background technique
Surface enhanced Raman spectroscopy (SERS) technology is a kind of important trace analysis detection means, can be extremely complex
Simple and clear spectral information can be obtained by only enhancing target molecule or group in system, make it possible Single Molecule Detection.
SERS technology to sample because can carry out nondestructive analysis, fingerprint characteristic, not contact that sample, required time be short, sample at present
The features such as aequum is small and become research hotspot, be widely used in pharmaceutical synthesis, archaeology, Gemstone Identification and forensic science etc.
Aspect.
On-site test be SERS development an important directions, at present there are many portable instrument, be badly in need of therewith
The highly sensitive portable SERS substrate to match.Therefore, develop the highly sensitive portable SERS substrate of one kind in various scene inspections
Have in survey and is greatly worth.
Currently, common portable SERS substrate has based on substrates such as capillary, paper, optical fiber, stainless pins, but these
The problems such as sensitivity is low, complicated for operation, stability is poor is individually present in portable SERS substrate.Acupuncture acupuncture needle is since the Western Han Dynastry,
Through the history for having more than 1,000 years.Silverware is often used in the detection arsenides drugs such as arsenic in ancient times, and 1974, Fleischmann
Et al. have found Surface enhanced Raman spectroscopy phenomenon in rough silver electrode surface.It is current studies have shown that your gold such as silver and gold
Category can amplify 1,000,000 times of Raman signal.
In addition, how uniformly to modify nano particle in metal surface is a key technology for constructing portable SERS substrate
Problem.High polymer binder is added mostly at present, process is complicated.In consideration of it, we are based on traditional acupuncture acupuncture needle and PVP is steady
Fixed nano particle prepares highly sensitive portable SERS substrate.
Summary of the invention
The technical problem to be solved by the present invention is to prepare a kind of highly sensitive portable SERS substrate based on acupuncture acupuncture needle
Preparation method simple and quick can be prepared this highly sensitive portable using the stable gold nano grain of acupuncture acupuncture needle and PVP
SERS substrate is suitable for various solution systems and detects, has high sensitivity and repeatability.
A kind of preparation method of the highly sensitive portable SERS substrate based on acupuncture acupuncture needle comprising following steps:
It (1) will be spare after the cleaning of acupuncture acupuncture needle;
(2) synthesis PVP stable gold nano grain;
(3) by after PVP stable gold nano grain eccentric cleaning, the gold nano grain that the 10-90% for original content is concentrated is molten
Glue;
It (4) will be through being impregnated in step (1) treated acupuncture acupuncture needle insertion gold nano particle colloidal sols;
(5) it will be inserted into measuring samples solution after the acupuncture acupuncture needle drying after step (4) are modified, utilize portable Raman
Spectrometer carries out SERS detection.
Further scheme, the cleaning of acupuncture acupuncture needle refers to first through acetone soak and ultrasound at least 30min in the step (1)
Afterwards, then with ethyl alcohol simultaneously ultrasound at least 30min is impregnated.
Further scheme, the synthetic method of PVP stable gold nano grain is as follows in the step (2):
(1) by HAuCl4Solution and ultrapure water mixing;
(2) when being heated to mixed liquor boiling, sodium citrate solution is added, keeps boiling and uniform stirring obtains AuNPs colloidal sol;
(3) it is separately added into sodium citrate solution, PVP solution and hydroxylamine hydrochloride solution into AuNPs colloidal sol, stirs evenly;
(4) HAuCl is added into step (3) resulting mixed liquor with the speed of 1ml/min4Solution is protected during being added dropwise
It holds and stirs the gold nano grain stable to get PVP.
Further scheme, acupuncture acupuncture needle is immersed in gold nano particle colloidal sols in the step (4), and the time of standing is
10-120 min。
Further scheme, the solvent in the measuring samples solution includes: water, ethyl alcohol, methanol, acetone, benzene class (benzene, first
Benzene, dimethylbenzene etc.), fat hydrocarbon (pentane, hexane, octane etc.), alicyclic hydrocarbon type (hexamethylene etc.), chlorinated hydrocarbons (chlorobenzene, dichloro
Methane, chloroform, dichloro-benzenes, carbon tetrachloride, tetrachloro-ethylene etc.), ethers (ether, propylene oxide etc.), lipid (methyl acetate, second
Acetoacetic ester, propyl acetate etc.), pyridine.
Highly sensitive portable SERS substrate prepared by the present invention based on acupuncture acupuncture needle, can realize well to various liquid
The highly sensitive detection of body, and there is preferable repeatability, the principles of science analysis are as follows:
One, between the nano particle on acupuncture acupuncture needle surface there are local surface coupled plasma and particle and acupuncture needle it
Between the polarization of existing surface plasma, increase SERS signal jointly, further improve the sensitivity of detection.
Two, PVP stable gold nano grain improves the stability of nano particle due to the presence of space surface steric hindrance,
And PVP is as a kind of high polymer binder, it is ensured that the stability of substrate.
Three, the presence of PVP ensures that the reproducibility of detection so that gold nano grain tends to intensive monolayer alignment.
The present invention develops the highly sensitive portable SERS substrate of one kind and has on the basis of traditional acupuncture acupuncture needle
Preferable reproducibility and stability.Sensitivity mainly is improved using the bimetallic coupling of acupuncture needle and gold nano grain,
The stability that substrate is improved using the space steric effect of PVP improves base using the dense arrangement between gold nano grain
The reproducibility at bottom.
The beneficial effects of the present invention are:
(1) present invention combines the stable gold nano grain of acupuncture acupuncture needle and PVP, SERS substrate is obtained, to improve
Detection sensitivity and repeatability.
(2) the substrate preparation method step is simple and practical, and performance is stablized, easy to carry, is conducive to be applied to reality
Production and it is practical in, and carry out commercialization transformation.
(3) what the present invention detected is various liquid systems, including inorganic solvent and organic solution, be can be widely applied to
The liquid detecting of various scenes.
(4) the resulting substrate of the present invention to malachite green, crystal violet, thiram, various pigments have higher sensitivity,
Stability, and there is good reproducibility, meet actually detected standard.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the stereoscan photograph in embodiment 1 by treated acupuncture acupuncture needle is immersed in gold nano grain self assembly;
Fig. 2 is digital photograph and the EDS elemental analysis of acupuncture acupuncture needle SERS substrate prepared by embodiment 1;
Fig. 3 is that acupuncture acupuncture needle SERS substrate prepared by embodiment 1 is used for the Raman that various liquid measuring samples are detected
Spectrogram.
Specific embodiment
The invention will be further described with reference to embodiments, but the present invention is not limited to following embodiments.
Embodiment 1:
(1) spare after cleaning acupuncture acupuncture needle ethyl alcohol and acetone repeatedly;
(2) gold nano grain that synthetic PVP is wrapped up is centrifuged (7000r) with ultrapure water to clean, is concentrated;
(3) acupuncture acupuncture needle is impregnated into 10 min in gold nano grain after concentration;Fig. 1 institute in its stereoscan photograph
Show, can learn that gold nano grain successfully modifies the surface in acupuncture acupuncture needle from Fig. 1.
(4) the acupuncture acupuncture needle modified is statically placed in 30 min in the measuring samples solution taken water as a solvent;Its number shines
Piece and EDS elemental analysis modify gold nano grain region as shown in Fig. 2, can be recognized from Fig. 2 by naked eyes on acupuncture acupuncture needle
(yellow), and there is gold and money noble metal in modified regions.
(5) acupuncture acupuncture needle is taken out, SERS detection is carried out with portable Raman, then by the raman spectrum of itself and standard sample
Compareed the classification to determine substance.
It is that raman spectrum is detected to the SERS of various measuring samples solution as shown in Figure 3, wherein measuring samples solution (a) is
The aqueous solution of lemon yellow, (b) be thiram acetone soln, be (c) chloroformic solution of 2,2- bipyridyl, be (d) 4- sulfydryl pyrrole
The ethanol solution of pyridine;From figure 3, it can be seen that it is prepared by the present invention based on acupuncture acupuncture needle SERS substrate to various measuring samples solution all
There is good detection effect.
Embodiment 2:
(1) spare after cleaning acupuncture acupuncture needle ethyl alcohol and acetone repeatedly;
(2) gold nano grain that synthetic PVP is wrapped up is centrifuged (7000r) with ultrapure water to clean, is concentrated;
(3) acupuncture acupuncture needle is impregnated into 20 min in gold nano grain after concentration;
(4) the acupuncture acupuncture needle modified is statically placed in using ethyl alcohol as 20 min in the solution of solvent;
(5) acupuncture acupuncture needle is taken out, SERS detection is carried out with portable Raman, then by the raman spectrum of itself and standard sample
Compareed the classification to determine substance.
Embodiment 3:
(1) spare after cleaning acupuncture acupuncture needle ethyl alcohol and acetone repeatedly;
(2) gold nano grain that synthetic PVP is wrapped up is centrifuged (7000r) with ultrapure water to clean, is concentrated;
(3) acupuncture acupuncture needle is impregnated into 25 min in gold nano grain after concentration;
(4) the acupuncture acupuncture needle modified is statically placed in using chloroform as 15 min in the solution of solvent;
(5) acupuncture acupuncture needle is taken out, SERS detection is carried out with portable Raman, then by the raman spectrum of itself and standard sample
Compareed the classification to determine substance.
Embodiment 4:
(1) spare after cleaning acupuncture acupuncture needle ethyl alcohol and acetone repeatedly;
(2) gold nano grain that synthetic PVP is wrapped up is centrifuged (7000r) with ultrapure water to clean, is concentrated;
(3) acupuncture acupuncture needle is impregnated into 30 min in gold nano grain after concentration;
(4) the acupuncture acupuncture needle modified is statically placed in using acetone as 10 min in the solution of solvent;
(5) acupuncture acupuncture needle is taken out, SERS detection is carried out with portable Raman, then by the raman spectrum of itself and standard sample
Compareed the classification to determine substance.
The above described is only a preferred embodiment of the present invention, not making any form to technical solution of the present invention
On limitation.Without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variations
Still in the range of technical solution of the present invention and belong to the range of claimed invention with improving.
Claims (5)
1. a kind of preparation method of the highly sensitive portable SERS substrate based on acupuncture acupuncture needle, it is characterised in that: including following step
It is rapid:
It (1) will be spare after the cleaning of acupuncture acupuncture needle;
(2) synthesis PVP stable gold nano grain;
(3) it by after PVP stable gold nano grain eccentric cleaning, is concentrated as the gold nano particle colloidal sols of original volume 10-90%;
It (4) will be through being impregnated in step (1) treated acupuncture acupuncture needle insertion gold nano particle colloidal sols;
(5) it will be inserted into measuring samples solution after the acupuncture acupuncture needle drying after step (4) are modified, utilize Portable Raman optical spectrum
Instrument carries out SERS detection.
2. the preparation method according to claim 1, it is characterised in that: the cleaning of acupuncture acupuncture needle refers in the step (1)
First through acetone soak and after ultrasound at least 30min, then with ethyl alcohol impregnate simultaneously ultrasound at least 30min.
3. the preparation method according to claim 1, it is characterised in that: PVP stable gold nano in the step (2)
The synthetic method of grain is as follows:
(1) by HAuCl4Solution and ultrapure water mixing;
(2) when being heated to mixed liquor boiling, sodium citrate solution is added, keeps boiling and uniform stirring obtains AuNPs colloidal sol;
(3) it is separately added into sodium citrate solution, PVP solution and hydroxylamine hydrochloride solution into AuNPs colloidal sol, stirs evenly;
(4) HAuCl is added into step (3) resulting mixed liquor with the speed of 1ml/min4Solution keeps stirring during being added dropwise
Mix the gold nano grain stable to get PVP.
4. the preparation method according to claim 1, it is characterised in that: acupuncture acupuncture needle is immersed in gold in the step (4)
In nano particle colloidal sol, the time of standing is 10-120min.
5. preparation method according to claim 1, it is characterised in that: the solvent in the measuring samples solution include: water,
Ethyl alcohol, methanol, acetone, benzene class, fat hydrocarbon, alicyclic hydrocarbon type, chlorinated hydrocarbons, ethers, lipid, pyridine.
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CN108918503A (en) * | 2018-07-27 | 2018-11-30 | 苏州工业职业技术学院 | It is a kind of based on needle body SERS substrate to the detection method of pesticide residues in fruits |
CN109060764B (en) * | 2018-08-23 | 2020-12-29 | 安徽中科赛飞尔科技有限公司 | Preparation method of functionalized SERS platform and application of functionalized SERS platform in ATP detection |
CN112697769A (en) * | 2020-12-10 | 2021-04-23 | 合肥学院 | Method for realizing on-site rapid SERS detection based on centrifugal self-assembly technology |
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CN105074427A (en) * | 2013-01-29 | 2015-11-18 | 惠普发展公司,有限责任合伙企业 | Apparatus having surface-enhanced spectroscopy elements on an exterior surface |
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