CN103495726B - A kind of surface treatment method of surface enhancement Raman spectroscopy substrate material - Google Patents
A kind of surface treatment method of surface enhancement Raman spectroscopy substrate material Download PDFInfo
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- CN103495726B CN103495726B CN201310478305.9A CN201310478305A CN103495726B CN 103495726 B CN103495726 B CN 103495726B CN 201310478305 A CN201310478305 A CN 201310478305A CN 103495726 B CN103495726 B CN 103495726B
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Abstract
The invention discloses a kind of surface treatment method of surface enhancement Raman spectroscopy substrate material, comprise the steps: that (1) is by metal nanoparticle and the mixing of appropriate amine substance; (2) appropriate time is stirred under proper temperature.The inventive method technique is simple, and processing method uses amine substance cost low, and consumption is few; This processing method operating procedure is stablized, reproducible.
Description
Technical field
The present invention relates to Raman spectrum detection field, relate to a kind of surface treatment method of surface enhancement Raman spectroscopy substrate material particularly.
Background technology
SERS is a kind of spectral technique of quick detection material surface molecule structure, and its main feature is the finger print information that can obtain rapidly trace materials in complex system, has the advantage such as high sensitivity and high accuracy.SERS technology not only plays an important role in the basic scientific researches such as DNA detection, the behavior of electrode surface Molecular Adsorption and bio-imaging, is also used widely in the practical field such as quality testing, food security, explosive, drugs, jewel and art work qualification.
Conventional surface-enhanced Raman spectrum active substrate material is mainly gold or silver nano-grain.People have successfully synthesized gold or the silver nano-grain of various pattern and size, and can be few as commercial surface enhancement Raman spectroscopy substrate material.This is because commercial surface enhancement Raman spectroscopy substrate material had not only needed to have higher Raman enhanced activity but also need to stablize preservation.The substrate material surface with higher Raman enhanced activity is general relatively cleaner, and surface energy is higher, and easily reuniting loses Raman enhanced activity; And stable substrate material surface is generally containing strong protective agent, these strong protective agents are adsorbed on substrate material surface and seriously hinder the enrichment of test substance at substrate material surface, cause base material to be difficult to strengthen the Raman signal of test substance.
With I
-(iodide ion) for strong protective agent be method [Yadong Yin et al.Nanoscale, 2012,4, the 2875-2878 of the synthesizing stable gold nano grain of class classics; Michael H.Huang et al.Chem.Eur.J.2011,17,9746 – 9752; Chad A.Mirkin et al.Nano Lett.2008,8,2526-2529], the gold nano grain that this class synthetic method obtains is highly stable, but the application in SERS is but restricted, if can by the I of the strong absorption on this stable gold nano grain surface
-suitably process, then can obtain the surface enhancement Raman spectroscopy substrate material of class I goods.
At present, the I of nano grain surface is processed
-two kinds of method for oxidation below main employing: (1) hydrogen peroxide oxidation method.Ohsaka, T. etc. (Ohsaka, T.et al.Anal.Chem.2006,78,1200 – 1205.) utilize hydrogen peroxide effectively can remove gold nano grain surface I
-ion.But Kauffmann, J.M. etc. (Kauffmann, J.M.et al.Electrochim.Acta1998,43,3467 – 3473) find, hydrogen peroxide oxidation effect is too strong, can by I
-whole removing gold oxide nano grain surface.Although institute is simple and practical in this way, gold nano grain surface I-effectively can be removed, and the gold nano grain surface coverage one deck oxide finally obtained, test substance effectively can not be adsorbed on this oxide surface, and Raman enhanced activity is still lower; (2) electrochemical oxidation process.ZQ Tian etc. (ZQ Tian et al.Anal.Chem.2008,80,5118 – 5125) utilize the I of electrochemical method gold oxide nano grain surface
-, by the I of strong adsorptivity
-be converted into the weakly stable species such as IO3-, but the method operating procedure is complicated, need to consume electric energy, and operation requirements is strict, treated gold nano grain surface is easy to again adsorb I
-or by I
-reject completely and do not generate IO
3-deng weakly stable species, cause gold nano grain surface too clean and can not preservation be stablized.
So exploitation new method prepares base material that storage stability and Raman enhanced activity have concurrently for the commercialization of SERS with popularly have important value.
Summary of the invention
The object of the present invention is to provide a kind of surface treatment method of easy gold nano grain, utilize amine substance to I
-the high stability of protection and the very poor metal nanoparticle of Raman enhanced activity carries out surface treatment; obtain the metal nanoparticle that a kind of storage stability and Raman enhanced activity have concurrently, solve the difficult problem that surface enhancement Raman spectroscopy substrate material storage stability and Raman enhanced activity are difficult to have concurrently.
Technical scheme of the present invention is as follows
A surface treatment method for surface enhancement Raman spectroscopy substrate material, comprises the steps:
(1) by metal nanoparticle and the mixing of appropriate amine substance;
(2) appropriate time is stirred.
Wherein, metal nanoparticle of the present invention comprises surface containing I
-gold nano grain.
Wherein, described mixing can be after metal nanoparticle is first dispersed in water, ethanol or DMF equal solvent, then mixes with amine substance;
Wherein, when metal nanoparticle is first dispersed in water, ethanol or DMF equal solvent, it preferably disperses ratio to be: nano particle mass fraction scope is in a solvent 0.0001-100wt%-;
Wherein, described amine substance comprises molecular formula and meets C
nh
2n+3n(8>=n>=0) material, comprise at least one in ammoniacal liquor, methylamine, ethamine, n-butylamine, n-octyl amine etc.
Wherein, the better condition of step (1) mol ratio between metal nanoparticle and amine substance is between 1:0.01 to 1:100.
Wherein, the better condition of step (2) mixing time is 10 minutes to 72 hours.
A kind of metal nanoparticle, is characterized in that: it is obtained by aforesaid method.
Metal nanoparticle after aforesaid method process is as the purposes of surface enhancement Raman spectroscopy substrate material.
Major advantage of the present invention is: 1) this processing method can make I
-the Raman of protection strengthens very weak metal nanoparticle and has higher Raman enhanced activity (as Fig. 4 and Fig. 5), higher dispersiveness (as Fig. 1 and Fig. 2) and good stability (as Fig. 3), can use as the commercial surface enhancement Raman spectroscopy substrate material of one; 3) this processing method does not use a large amount of solvent and optical, electrical related equipment, simple to operate, with low cost.4) this processing method operating procedure is stablized, reproducible.
Accompanying drawing explanation
Fig. 1. before embodiment 1 processes scanning electron microscope (SEM) photograph (a) process of front and back gold nano grain, b) after process), illustrate that size and pattern change do not occur to modify rear gold nano grain, and better dispersed.
Fig. 2. the size distribution plot of gold nano grain before and after embodiment 1 processes, illustrates that after modifying, gold nano grain is better dispersed.
Fig. 3. the surface potential distribution map of gold nano grain before and after embodiment 1 processes, the surface potential absolute value of gold nano grain is greater than 30, illustrates that after modifying, gold nano grain stability is better.
Fig. 4. embodiment 10 processes the SERS figure of front gold nano grain to the 1ppm malachite green aqueous solution, 162 centimetres
-1for the characteristic peak of gold-iodine key, before process is described, gold nano grain does not have humidification to malachite green.
Fig. 5. embodiment 10 processes the SERS figure of rear gold nano grain to the 1ppm malachite green aqueous solution, and after process is described, gold nano grain has better humidification to malachite green.
Detailed description of the invention
Embodiment 1
(1) get 50mL round-bottomed flask, add 19mL ultra-pure water successively, 2mg gold chloride, 1mL sodium citrate aqueous solution (5mM), stir 5-10min to settled solution;
(2) aqueous solution (0.1M) of 1mL sodium borohydride is added;
(3) leave standstill after stirring at room temperature 4h, products therefrom called after A, is stored in 4 DEG C;
(4) get 500mL round-bottomed flask, add 300mL ultra-pure water successively, 600mg gold chloride, 3g PVP stirs 15-20min to settled solution;
(5) KI (the 0.25M aqueous solution, 25mL) is added successively, ascorbic acid (the 0.15M aqueous solution, 20mL), A (0.05mL)
(6) leave standstill after stirring at room temperature 15min, products therefrom called after B;
(7) in B, 0.001mL concentrated ammonia liquor (25% aqueous solution) is added, stirring at room temperature 30min, product called after C.
The results are shown in Figure 1, Fig. 2 and Fig. 3
Embodiment 2
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 10mL concentrated ammonia liquor (25% aqueous solution) is added, stirring at room temperature 30min.
Embodiment 3
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 0.001mL methylamine water solution (25%) is added, stirring at room temperature 10min.
Embodiment 4
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 0.001mL methylamine water solution (25%) is added, stirring at room temperature 12h
Embodiment 5
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 0.001mL methylamine water solution (25%) is added, stirring at room temperature 72h
Embodiment 6
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 10mL methylamine water solution (25%) is added, stirring at room temperature 12h
Embodiment 7
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 0.001mL n-butylamine is added, stirring at room temperature 12h.
Embodiment 8
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, 10mL n-butylamine is added, stirring at room temperature 12h.
Embodiment 9
(1) according to embodiment 1 step (1)-(6) sintetics B;
(2) in product B, the positive heptyl amice of 0.001mL is added, stirring at room temperature 12h.
Embodiment 10
(1) according to step (1) in embodiment 1-(6) sintetics B;
(2) get B centrifugal concentrating 1 time (4000 revs/min, 3 minutes) in 0.2mL embodiment 1, with liquid-transfering gun sucking-off 0.19mL supernatant fluid, leave 0.01mL lyosol.
(3) 0.01mL lyosol is dripped on monocrystalline silicon piece (4x4mm), naturally dry.
(4) use Raman spectrometer to detect, obtain processing the SERS figure of front Au nano particle as blank.Testing conditions is as follows: U.S. DeltaNu company Inspector Portable Raman spectrometer, optical maser wavelength 785nm, laser power 60mW, sweep time 1s, scanning times 1 time.
(5) get the 0.01mL1ppm malachite green aqueous solution to drip on the silicon chip after drying in the present embodiment step (3).
(6) use Raman spectrometer to detect, obtain processing the SERS figure of front Au nano particle to the 1ppm malachite green aqueous solution.Testing conditions is with the present embodiment step (4).
(7) get C in 0.2mL embodiment 1, obtain processing rear Au nano particle as Au nano particle after the SERS figure of blank and process to the SERS figure of the 1ppm malachite green aqueous solution according to the present embodiment step (2)-(6)
The results are shown in Figure 4 and Fig. 5.
Claims (7)
1. a surface treatment method for surface enhancement Raman spectroscopy substrate material, comprises the steps:
(1) by metal nanoparticle and the mixing of appropriate amine substance;
(2) appropriate time is stirred;
Described metal nanoparticle is that surface is containing I
-gold nano grain.
2. the surface treatment method of a kind of surface enhancement Raman spectroscopy substrate material as claimed in claim 1, is characterized in that: described amine substance comprises molecular formula and meets C
nh
2n+3n, the wherein material of 8>=n>=0.
3. the surface treatment method of a kind of surface enhancement Raman spectroscopy substrate material as claimed in claim 2, is characterized in that: described amine substance comprises at least one in ammoniacal liquor, methylamine, ethamine, n-butylamine, n-octyl amine.
4. the surface treatment method of a kind of surface enhancement Raman spectroscopy substrate material as claimed in claim 1, is characterized in that: the better condition of step (1) mol ratio between metal nanoparticle and amine substance is between 1:0.01 to 1:100.
5. the surface treatment method of a kind of surface enhancement Raman spectroscopy substrate material as claimed in claim 1, is characterized in that: the better condition of step (2) mixing time is between 10 minutes to 72 hours.
6. a metal nanoparticle, is characterized in that: it is obtained by the method for any one of claim 1 to 5.
7. the metal nanoparticle after the method process according to any one of claim 1 to 5 is as the purposes of surface enhancement Raman spectroscopy substrate material.
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| JP2007154292A (en) * | 2005-12-08 | 2007-06-21 | Mitsubishi Materials Corp | Method for producing silver particle, silver particle-containing composition containing the silver particle and its use |
| US20090201496A1 (en) * | 2008-02-11 | 2009-08-13 | Shuit-Tong Lee | Surface-enhanced raman scattering based on nanomaterials as substrate |
| KR101066545B1 (en) * | 2008-09-08 | 2011-09-22 | 한국생명공학연구원 | Metal Nanoparticles of Various Sizes and Shapes Having Functional Groups and Method for Preparing the Same |
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