CN107216049A - A kind of preparation method of plasticiser detection SERS substrates - Google Patents
A kind of preparation method of plasticiser detection SERS substrates Download PDFInfo
- Publication number
- CN107216049A CN107216049A CN201710414742.2A CN201710414742A CN107216049A CN 107216049 A CN107216049 A CN 107216049A CN 201710414742 A CN201710414742 A CN 201710414742A CN 107216049 A CN107216049 A CN 107216049A
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- China
- Prior art keywords
- silver
- sheet glass
- detection
- plasticiser
- sers substrates
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Abstract
The present invention relates to a kind of preparation method of plasticiser detection SERS substrates.Methods described is：A:Sheet glass is soaked into 2~more than 3h with chromic acid, ultra-pure water is cleaned；B：Sheet glass after cleaning is immersed in silver-colored ammonium salt solution, control time and temperature, occurs silver mirror reaction, plate a thin layer of silver layer and silver mirror sheet glass is made；C：Silver mirror sheet glass is placed in hydrophobically modified liquid and soaks 1 15h progress silver layer surface modifications, natural air drying is taken out and obtains a kind of described plasticiser detection SERS substrates.Raman produced by the present invention strengthens substrate, required detection droplet size can as little as 1.5 μ L, substrate surface can carry out Multi-point detection.Meanwhile, testing molecule does not adsorb only on metal-sol particle surface, and the silverskin that nano-particle is also modified with surface is acted, and is formed new enhancing " focus ", be further enhancing the detection of Raman scattering signal.
Description
Technical field
The present invention relates to a kind of preparation method of plasticiser detection SERS substrates.
Background technology
Plasticiser is also known as " plasticizer ", is widely used in the industry, is mainly used in the products such as plastics, rubber, binder
In, to increase the suppleness of product.Health ministry points out plasticiser non-food stuff additive, and long-term consumption can be carcinogenic.But be
It is cost-effective, play in the product emulsification, thickening etc. act on and make it is all kinds of uniformly exist to improve mouthfeel in food, plastify
Agent is illegally added in beverage, grease, flavoring essence, cream, dairy products etc..In recent years it is even more to report Taiwan modeling again and again
Agent milk tea event, Hunan drunkard's event and baby milk powder mix modeling event etc..
At present, the annual production of global plasticiser has reached more than 900 ten thousand tons, and more than 80% is phthalate material,
Other 20% includes the multiclass compounds such as many esters of gallic acid of benzene, polyalcohol esters.The most country of plasticiser usage amount is China, is accounted for
World's plasticiser uses the 43% of total amount, next to that West Europe and the U.S..With phthalate material in industrial and agricultural production and
Widely using in life, it has become the organic pollution of globalization, is referred to as " second global pollution by polychlorinated biphenyles
Thing ".At present, the detection of plasticiser mainly has high performance liquid chromatography, gas chromatography-mass spectrography, extraction-gas-chromatography combination
Etc. technology, the plasticiser in the materials such as beverage, white wine, grease can be preferably detected, but be due to that the limitation of method is required for
By more troublesome sample making course, on the other hand, in sample making course, plasticiser is also possible to loss, so as to influence detection
Accuracy., can be directly in testing sample and Raman spectrum is to carry out discrimination detection by molecular vibration " dactylogram "
Middle detection, without sample preparation, compared to existing common method, it is accurate more to facilitate.
Surface-enhanced Raman effects are to adsorb chemical substance in textured metal by the mechanism of electromagnetic field and electro transfer
Surface, so as to greatly strengthen the behavior of the raman spectrum strength of detected material.SERS is in bio-sensing, list
There is important application in the fields such as cell detection, environment.Researchers prepare many colloidal sol shape nano particles, and high degree increases
Strong Ramam effect, also reduces test limit.But these surface Raman enhancement colloidal sols easily condense, Raman enhancing poor repeatability, very
Hardly possible is used for practical application.On the other hand, during Raman detection, what is used is usually the aqueous solution, and conventional base material is aluminium flake, sheet glass
Deng, the contact angle of the aqueous solution is smaller, easily diffusion.
It is contemplated that a kind of super hydrophobic surface Raman enhancing base materials are announced, will when particularly detecting aqueous solution determinand
Polycondensation plays a part of concentration in some while determinand drops in evaporation with metal-sol mixed liquor, reduces the same of test limit
Shi Tigao reappearances.
The content of the invention
Shortcoming of the present invention for existing surface Raman enhancement substrate is improved that there is provided a kind of plasticiser detection SERS
The preparation method of substrate, has the advantages that hypersensitivity and good reappearance.Preparation method is simple, can be widely applied to
The fields such as large biological molecule, the residual, environment of agriculture.
The purpose of the present invention is achieved through the following technical solutions：
A:Sheet glass is soaked into 2~more than 3h with chromic acid, ultra-pure water is cleaned.
B：Sheet glass after cleaning is immersed in silver-colored ammonium salt solution, control time and temperature, occurs silver mirror reaction, plate one
Silver mirror sheet glass is made in the very thin silver layer of layer.
C：Silver mirror sheet glass is placed in hydrophobically modified liquid and soaks 1-15h progress silver layer surface modifications, natural air drying is taken out
Obtain a kind of described plasticiser detection SERS substrates.
Described silver-colored ammonium salt solution is：The concentration of silver nitrate is 0.05~0.25mol/L, the concentration of ammoniacal liquor for 0.3~
0.85mol/L。
Described silver mirror reaction control condition is：Time 5min~20min, 50~90 DEG C of temperature.
Described surface hydrophobicity modifying agent is：One in perfluor lauryl mercaptan, lauryl mercaptan, Stearyl mercaptan
The mixing of kind or two kinds of arbitrary proportions.
Raman produced by the present invention strengthens substrate, required detection droplet size can as little as 1.5 μ L, substrate surface can enter
Row Multi-point detection.The hypersensitive detection performance of the Raman enhancing base materials material has benefited from the ultra-hydrophobicity of substrate surface, surface
After drop evaporation to be measured, the concentration building-up effect of metal-sol and testing molecule is formed.Meanwhile, testing molecule does not adsorb only on gold
Belong to sol particles surface, the silverskin that nano-particle is also modified with surface is acted, form new enhancing " focus ", further increase
The strong detection of Raman scattering signal.
Brief description of the drawings
Fig. 1 is contact angle photo of the plasticiser detection SERS substrates to water of embodiment 1.
Fig. 2 is contact angle photo of the plasticiser detection SERS substrates to water of embodiment 2.
Fig. 3 is with 10^-9The Raman spectrogram that mol/L R6G measure for detection solution in the base material prepared by example 1.It is used
R6G volumes are 1.5 μ L.
Fig. 4 is 10^-3Mol/L diisobutyl phthalates（DIBP, commonly uses one of plasticiser）It is to detect solution in example
The Raman spectrogram that base material prepared by 2 is measured.
Fig. 5 is that 5 μ L DIBP solution and 1.5 μ L silver sols dry front and rear microphotograph comparison diagram.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
The sheet glass (1cm*1cm) of well cutting is soaked into 2h with chromic acid, ultra-pure water is cleaned；Added in 5mL centrifuge tube
In the silver-colored ammonium salt solution that 0.05mol/L silver nitrate solution and concentration is configured to for 0.35mol/L ammoniacal liquor, the Portugal of 1 drop 6% is added
Grape sugar juice simultaneously shakes up, and is put into sheet glass, 15min is heated under 75 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror glass
After piece, dried with nitrogen, the self-assembled modified 12h in lauryl mercaptan, take out, keep flat, dried in nitrogen stream；It can be moulded
SERS substrates are used in agent detection.C：Silver mirror sheet glass is placed in hydrophobically modified liquid and soaks 1-15h progress silver layer surface modifications, is taken
Go out natural air drying.
Embodiment 2
The sheet glass (1cm*1cm) of well cutting is soaked into 3h with chromic acid, ultra-pure water is cleaned；Concentration is added in 5mL centrifuge tube
In the silver-colored ammonium salt solution that the ammoniacal liquor for being 0.55mol/L for 0.2mol/L silver nitrate solution and concentration is configured to, the Portugal of 1 drop 6% is added
Grape sugar juice simultaneously shakes up, and is put into sheet glass, 10min is heated under 80 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror glass
After piece, dried in nitrogen stream, self-assembled modified 1h in stearylmercaptan solution takes out, kept flat, natural air drying；It can be surpassed
Hydrophobic surface strengthens Raman base material.
Embodiment 3
The sheet glass (1cm*1cm) of well cutting is soaked into more than 2h with chromic acid, ultra-pure water is cleaned；Added in 5mL centrifuge tube
In the silver-colored ammonium salt solution that the ammoniacal liquor that concentration is 0.25mol/L silver nitrate solutiones and concentration is 0.45mol/L is configured to, 1 drop 6% is added
Glucose solution and shake up, be put into sheet glass, under 80 DEG C of water-bath heat 15min silver mirror sheet glass is made；Form silver mirror
After sheet glass, dried with nitrogen, the self-assembled modified 12h in Stearyl mercaptan and lauryl mercaptan mixed solution takes
Go out, dried in nitrogen stream；It can obtain plasticiser detection SERS substrates.
Embodiment 4
The sheet glass (1cm*1cm) of well cutting is soaked into 2h with chromic acid, ultra-pure water is cleaned；Added in 5mL centrifuge tube dense
In the silver-colored ammonium salt solution that the ammoniacal liquor that degree is 0.25mol/L silver nitrate solutiones and concentration is 0.85mol/L is configured to, 1 drop 6% is added
Glucose solution simultaneously shakes up, and is put into sheet glass, 15min is heated under 75 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror glass
After glass piece, dried, the self-assembled modified 10h in perfluor lauryl mercaptan solution, taken out with nitrogen, dried in nitrogen stream；
Obtain plasticiser detection SERS substrates.
Embodiment 5
The sheet glass (1cm*1cm) of well cutting is soaked into 3h with chromic acid, ultra-pure water is cleaned；Concentration is added in 5mL centrifuge tube
In the silver-colored ammonium salt solution that the ammoniacal liquor for being 0.3mol/L for 0.1mol/L silver nitrate solutiones and concentration is configured to, the grape of 1 drop 6% is added
Sugar juice simultaneously shakes up, and is put into sheet glass, 10min is heated under 75 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror sheet glass
Afterwards, dried, the self-assembled modified 10h in perfluor lauryl mercaptan solution, taken out with nitrogen, dried in nitrogen stream；It can obtain
SERS substrates are used in plasticiser detection.
Embodiment 6
The sheet glass (1cm*1cm) of well cutting is soaked into 4h with chromic acid, ultra-pure water is cleaned；Concentration is added in 5mL centrifuge tube
In the silver-colored ammonium salt solution that the ammoniacal liquor for being 0.3mol/L for L 0.15mol/L silver nitrate solutiones and concentration is configured to, the Portugal of 1 drop 6% is added
Grape sugar juice simultaneously shakes up, and is put into sheet glass, 15min is heated under 65 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror glass
After piece, dried, the self-assembled modified 10h in stearyl mercaptan solutions, taken out with nitrogen, dried in nitrogen stream；It can obtain
SERS substrates are used to plasticiser detection.
The concentration of the silver nitrate of embodiment 74 is 0.05~0.25mol/L, and the concentration of ammoniacal liquor is 0.3~0.85mol/L.
The sheet glass (1cm*1cm) of well cutting is soaked into 5h with chromic acid, ultra-pure water is cleaned；Added in 5mL centrifuge tube
Concentration is 0.2mol/L silver nitrate solutiones and during concentration is the silver-colored ammonium salt solution that 0.55mol/L is configured to, and adds the grape of 1 drop 6%
Sugar juice simultaneously shakes up, and is put into sheet glass, 15min is heated under 65 DEG C of water-bath silver mirror sheet glass is made；Form silver mirror sheet glass
Afterwards, dried, the self-assembled modified 10h in lauryl mercaptan and Stearyl mercaptan mixed solution, taken out, nitrogen with nitrogen
Dried in stream；It can obtain plasticiser detection SERS substrates.
Claims (4)
1. a kind of preparation method of plasticiser detection SERS substrates, it is characterised in that methods described comprises the following steps：
A:Sheet glass is soaked into 2~more than 3h with chromic acid, ultra-pure water is cleaned；
B：Sheet glass after cleaning is immersed in silver-colored ammonium salt solution, control time and temperature, occurs silver mirror reaction, plating last layer is thin
Silver mirror sheet glass is made in thin silver layer；
C：Silver mirror sheet glass is placed in hydrophobically modified liquid and soaks 1-15h progress silver layer surface modifications, natural air drying is taken out and obtains
SERS substrates are used in a kind of described plasticiser detection.
2. the preparation method of a kind of plasticiser detection SERS substrates according to claim 1, it is characterised in that described
Silver mirror reaction control condition is：Time 5min~20min, 50~90 DEG C of temperature.
3. the preparation method of a kind of plasticiser detection SERS substrates according to claim 1, it is characterised in that described
Silver-colored ammonium salt solution is：The concentration of silver nitrate is 0.05~0.25mol/L, and the concentration of ammoniacal liquor is 0.3~0.85mol/L.
4. the preparation method of a kind of plasticiser detection SERS substrates according to claim 1, it is characterised in that described
Surface hydrophobicity modifying agent be：One or both of perfluor lauryl mercaptan, lauryl mercaptan, Stearyl mercaptan arbitrarily compare
The mixing of example.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710414742.2A CN107216049A (en) | 2017-06-05 | 2017-06-05 | A kind of preparation method of plasticiser detection SERS substrates |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710414742.2A CN107216049A (en) | 2017-06-05 | 2017-06-05 | A kind of preparation method of plasticiser detection SERS substrates |
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| CN107216049A true CN107216049A (en) | 2017-09-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109520992A (en) * | 2018-11-08 | 2019-03-26 | 南京光声超构材料研究院有限公司 | A kind of SERS substrate of bromination silver nanowires and preparation method thereof |
| CN109540867A (en) * | 2018-11-30 | 2019-03-29 | 东南大学 | A kind of plasticiser Raman spectra detection process based on molecular engram nano fibrous membrane |
| CN111770837A (en) * | 2018-01-15 | 2020-10-13 | 南洋理工大学 | Superhydrophobic platform for sensing urine metabolites and toxins |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111770837A (en) * | 2018-01-15 | 2020-10-13 | 南洋理工大学 | Superhydrophobic platform for sensing urine metabolites and toxins |
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| CN109520992A (en) * | 2018-11-08 | 2019-03-26 | 南京光声超构材料研究院有限公司 | A kind of SERS substrate of bromination silver nanowires and preparation method thereof |
| CN109520992B (en) * | 2018-11-08 | 2021-02-05 | 南京光声超构材料研究院有限公司 | SERS substrate of silver bromide nanowire and preparation method thereof |
| CN109540867A (en) * | 2018-11-30 | 2019-03-29 | 东南大学 | A kind of plasticiser Raman spectra detection process based on molecular engram nano fibrous membrane |
| CN109540867B (en) * | 2018-11-30 | 2021-07-27 | 东南大学 | Plasticizer Raman spectrum detection method based on molecularly imprinted nanofiber membrane |
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Application publication date: 20170929 |