CN106990092A - A kind of preparation method of the highly sensitive portable SERS substrates based on acupuncture acupuncture needle - Google Patents
A kind of preparation method of the highly sensitive portable SERS substrates based on acupuncture acupuncture needle Download PDFInfo
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- CN106990092A CN106990092A CN201710250359.8A CN201710250359A CN106990092A CN 106990092 A CN106990092 A CN 106990092A CN 201710250359 A CN201710250359 A CN 201710250359A CN 106990092 A CN106990092 A CN 106990092A
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- 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
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Abstract
The invention discloses a kind of preparation method of the highly sensitive portable SERS substrates based on acupuncture acupuncture needle, it comprises the following steps：It is standby after acupuncture acupuncture needle is cleaned；Synthesize the stable gold nano grains of PVP；After gold nano grain eccentric cleaning stable PVP, 10 90% gold nano particle colloidal sols for original content are concentrated；It will be soaked in acupuncture acupuncture needle insertion gold nano particle colloidal sols after processing；By in insertion measuring samples solution after the acupuncture acupuncture needle drying after modification, SERS detections are carried out 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 PVP space steric effect, the reappearance of substrate is improved using the dense arrangement between gold nano grain.Its preparation method is simple, is easy to carry, and suitable among any liquid environment.
Description
Technical field
The invention belongs to the technical field of chemical composition detection, and in particular to a kind of based on the highly sensitive portable of acupuncture acupuncture needle
The preparation method of formula SERS substrates.
Background technology
SERS（SERS）Technology is a kind of important trace analysis detection means, can be extremely complex
Only strengthening target molecule or group in system just can obtain simple and clear spectral information, make it possible Single Molecule Detection.
Current SERS technologies to sample because can carry out nondestructive analysis, fingerprint characteristic, not contact that sample, required time be short, sample
The features such as aequum is small and as study hotspot, be widely used in pharmaceutical synthesis, archaeology, Gemstone Identification and forensic science etc.
Aspect.
Site Detection is an important directions of SERS development, has there is a variety of portable instruments at present, is badly in need of therewith
The highly sensitive portable SERS substrates matched.Therefore, a kind of highly sensitive portable SERS substrates are developed in various scene inspections
Have in survey and be greatly worth.
At present, common portable SERS substrates have based on substrates such as capillary, paper, optical fiber, stainless pins, but these
The problems such as low sensitivity, complex operation, stability are poor is individually present in portable SERS substrates.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 arsenide drugs, Fleischmann in 1974 such as detection arsenic in ancient times
Et al. be found that SERS phenomenon in rough silver electrode surface.Current research shows your gold such as silver and gold
Category can amplify 1,000,000 times of Raman signal.
In addition, it is a key technology for constructing portable SERS substrates that nano particle how is uniformly modified in metal surface
Problem.Add high polymer binder 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 substrates.
The content of the invention
The technical problem to be solved in the present invention is to prepare a kind of highly sensitive portable SERS substrates based on acupuncture acupuncture needle
Preparation method, using acupuncture acupuncture needle and PVP stable gold nano grain can with it is simple and quick prepare it is this highly sensitive portable
SERS substrates, it is adaptable to various solution system detections, with high sensitivity and repeatability.
A kind of preparation method of the highly sensitive portable SERS substrates based on acupuncture acupuncture needle, it comprises the following steps：
（1）It is standby after acupuncture acupuncture needle is cleaned；
（2）Synthesize the stable gold nano grains of PVP；
（3）After gold nano grain eccentric cleaning stable PVP, the gold nano particle colloidal sols of the 10-90% for original content are concentrated；
（4）Will be through step（1）Soaked in acupuncture acupuncture needle insertion gold nano particle colloidal sols after processing；
（5）Will be through step（4）After acupuncture acupuncture needle drying after modification in insertion measuring samples solution, Portable Raman optical spectrum is utilized
Instrument carries out SERS detections.
Further scheme, the step（1）Middle acupuncture acupuncture needle cleaning refers to first through acetone soak and ultrasound at least 30min
Afterwards, then with ethanol soak and ultrasound at least 30min.
Further scheme, the step（2）The synthetic method of gold nano grain stable middle PVP is as follows：
（1）By HAuCl4Solution and ultra-pure water mixing；
（2）When being heated to mixed liquor boiling, sodium citrate solution is added, boiling is kept and uniform stirring obtains AuNPs colloidal sols；
（3）Sodium citrate solution, PVP solution and hydroxylamine hydrochloride solution are separately added into AuNPs colloidal sols, is stirred；
（4）With 1ml/min speed toward step（3）HAuCl is added in the mixed liquor of gained4Solution, keeps stirring during dropwise addition
Mix, produce the stable gold nano grains of PVP.
Further scheme, the step（4）Middle acupuncture acupuncture needle is immersed in gold nano particle colloidal sols, and the time of standing is
10-120 min。
Solvent in further scheme, the measuring samples solution includes：Water, ethanol, 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, expoxy propane etc.）, lipid（Methyl acetate, second
Acetoacetic ester, propyl acetate etc.）, pyridine.
Highly sensitive portable SERS substrates based on acupuncture acupuncture needle prepared by the present invention, can be realized to various liquid well
The highly sensitive detection of body, and with preferably repeatability, the analysis of its principles of science is：
First, there is local surface coupled plasma between the nano particle on acupuncture acupuncture needle surface, and deposited between particle and acupuncture needle
Surface plasma body polarization, SERS signal is increased jointly, the sensitivity of detection is further increased.
2nd, gold nano grain stable PVP, due to the presence of space surface steric hindrance, improves the stability of nano particle,
And PVP is used as a kind of high polymer binder, it is ensured that the stability of substrate.
3rd, PVP presence so that gold nano grain tends to intensive monolayer alignment, ensures that the reappearance of detection.
The present invention develops a kind of highly sensitive portable SERS substrates and had on the basis of traditional acupuncture acupuncture needle
Preferable reappearance and stability.The bimetallic coupling of acupuncture needle and gold nano grain is mainly used to improve sensitivity,
The stability of substrate is improved using PVP space steric effect, base is improved using the dense arrangement between gold nano grain
The reappearance at bottom.
The beneficial effects of the present invention are：
（1）Acupuncture acupuncture needle and the stable gold nano grains of PVP are combined by the present invention, SERS substrates are obtained, so as to improve detection
Sensitivity and repeatability.
（2）The substrate preparation method step is simple and practical, and performance is stable, is easy to carry, is conducive to being applied to reality
Production and practicality among, and carry out commercialization transformation.
（3）What the present invention was detected is various liquid systems, including inorganic solvent and organic solution, be can be widely applied to
The liquid detecting of various scenes.
（4）Substrate obtained by the present invention have to malachite green, crystal violet, thiram, various pigments higher sensitivity,
Stability, and with good reappearance, meet actually detected standard.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the stereoscan photograph that the acupuncture acupuncture needle after processing is immersed in in embodiment 1 gold nano grain self assembly；
Fig. 2 is digital photograph and the EDS elementary analyses of acupuncture acupuncture needle SERS substrates prepared by embodiment 1；
Fig. 3 is that acupuncture acupuncture needle SERS substrates prepared by embodiment 1 are used for the Raman spectrogram that various liquid measuring samples are detected.
Embodiment
The invention will be further described with reference to embodiments, but the present invention is not limited to following embodiments.
Embodiment 1:
（1）It is standby after acupuncture acupuncture needle is cleaned repeatedly with ethanol and acetone；
（2）The synthetic PVP gold nano grains wrapped up are centrifuged with ultra-pure water（7000r）Cleaning, concentration；
（3）By 10 min in the gold nano grain of acupuncture acupuncture needle immersion after concentration；In its stereoscan photograph shown in Fig. 1, from
It can learn that gold nano grain successfully modifies the surface in acupuncture acupuncture needle in Fig. 1.
(4) the acupuncture acupuncture needle modified is statically placed in 30 min in the measuring samples solution using water as solvent；Its number shines
Piece and EDS elementary analyses from Fig. 2 as shown in Fig. 2 can pass through modification gold nano grain region on naked eyes identification acupuncture acupuncture needle
（Yellow）, and in the presence of gold and money noble metal in modified regions.
（5）Acupuncture acupuncture needle is taken out, SERS detections are carried out with portable Raman, then by its Raman spectrogram with standard sample
Compareed to determine the classification of material.
It is that Raman spectrogram 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) is the acetone soln of thiram, and (c) is the chloroformic solution of 2,2- bipyridyls, and (d) is 4- sulfydryl pyrroles
The ethanol solution of pyridine；From figure 3, it can be seen that the present invention prepare based on acupuncture acupuncture needle SERS substrates to various measuring samples solution all
There are good Detection results.
Embodiment 2:
（1）It is standby after acupuncture acupuncture needle is cleaned repeatedly with ethanol and acetone；
（2）The synthetic PVP gold nano grains wrapped up are centrifuged with ultra-pure water（7000r）Cleaning, concentration；
（3）By 20 min in the gold nano grain of acupuncture acupuncture needle immersion after concentration；
（4）20 min during the acupuncture acupuncture needle modified is statically placed in using ethanol as the solution of solvent；
（5）Acupuncture acupuncture needle is taken out, SERS detections are carried out with portable Raman, then by the Raman spectrogram progress of itself and standard sample
Compare to determine the classification of material.
Embodiment 3:
（1）It is standby after acupuncture acupuncture needle is cleaned repeatedly with ethanol and acetone；
（2）The synthetic PVP gold nano grains wrapped up are centrifuged with ultra-pure water（7000r）Cleaning, concentration；
（3）By 25 min in the gold nano grain of acupuncture acupuncture needle immersion after concentration；
（4）15 min during the acupuncture acupuncture needle modified is statically placed in using chloroform as the solution of solvent；
（5）Acupuncture acupuncture needle is taken out, SERS detections are carried out with portable Raman, then by the Raman spectrogram progress of itself and standard sample
Compare to determine the classification of material.
Embodiment 4:
（1）It is standby after acupuncture acupuncture needle is cleaned repeatedly with ethanol and acetone；
（2）The synthetic PVP gold nano grains wrapped up are centrifuged with ultra-pure water（7000r）Cleaning, concentration；
（3）By 30 min in the gold nano grain of acupuncture acupuncture needle immersion after concentration；
（4）10 min during the acupuncture acupuncture needle modified is statically placed in using acetone as the solution of solvent；
（5）Acupuncture acupuncture needle is taken out, SERS detections are carried out with portable Raman, then by the Raman spectrogram progress of itself and standard sample
Compare to determine the classification of material.
The above described is only a preferred embodiment of the present invention, not making any form to technical scheme
On limitation.Without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
With the scope for improving still in the range of technical scheme and belonging to claimed invention.
Claims (5)
1. a kind of preparation method of the highly sensitive portable SERS substrates based on acupuncture acupuncture needle, it is characterised in that：Including following step
Suddenly：
（1）It is standby after acupuncture acupuncture needle is cleaned；
（2）Synthesize the stable gold nano grains of PVP；
（3）After gold nano grain eccentric cleaning stable PVP, the gold nano particle colloidal sols of the 10-90% for original content are concentrated；
（4）Will be through step（1）Soaked in acupuncture acupuncture needle insertion gold nano particle colloidal sols after processing；
（5）Will be through step（4）After acupuncture acupuncture needle drying after modification in insertion measuring samples solution, Portable Raman optical spectrum is utilized
Instrument carries out SERS detections.
2. the preparation method according to claim 1, it is characterised in that：The step（1）Middle acupuncture acupuncture needle cleaning refers to
First through after acetone soak and ultrasound at least 30min, then with ethanol immersion simultaneously ultrasound at least 30min.
3. the preparation method according to claim 1, it is characterised in that：The step（2）Gold nano stable middle PVP
The synthetic method of grain is as follows：
（1）By HAuCl4Solution and ultra-pure water mixing；
（2）When being heated to mixed liquor boiling, sodium citrate solution is added, boiling is kept and uniform stirring obtains AuNPs colloidal sols；
（3）Sodium citrate solution, PVP solution and hydroxylamine hydrochloride solution are separately added into AuNPs colloidal sols, is stirred；
（4）With 1ml/min speed toward step（3）HAuCl is added in the mixed liquor of gained4Solution, keeps stirring during dropwise addition
Mix, produce the stable gold nano grains of PVP.
4. the preparation method according to claim 1, it is characterised in that：The step（4）Middle acupuncture acupuncture needle is immersed in gold
In nano particle colloidal sol, the time of standing is 10-120min.
5. preparation method according to claim 1, it is characterised in that：Solvent in the measuring samples solution includes：Water,
Ethanol, methanol, acetone, benzene class, fat hydrocarbon, alicyclic hydrocarbon type, chlorinated hydrocarbons, ethers, lipid, pyridine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109060764A (en) * | 2018-08-23 | 2018-12-21 | 安徽中科赛飞尔科技有限公司 | A kind of SERS platform preparation method of functionalization and its detection application to ATP |
| 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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| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109060764A (en) * | 2018-08-23 | 2018-12-21 | 安徽中科赛飞尔科技有限公司 | A kind of SERS platform preparation method of functionalization and its detection application to ATP |
| 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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