CN101294904B - Production method of surface reinforced Raman scattering substrate - Google Patents
Production method of surface reinforced Raman scattering substrate Download PDFInfo
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- CN101294904B CN101294904B CN2008100385367A CN200810038536A CN101294904B CN 101294904 B CN101294904 B CN 101294904B CN 2008100385367 A CN2008100385367 A CN 2008100385367A CN 200810038536 A CN200810038536 A CN 200810038536A CN 101294904 B CN101294904 B CN 101294904B
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Abstract
The invention provides a method for preparing a surface enhanced Raman scattering base, and relates to the laser Raman field and the biochemical analysis detection field. The method is characterized in that a sodium polyacrylate solution with certain concentration is mixed with a silver solution to improve the surface enhanced Raman scattering base. The base prepared by adopting the method has excellent spectrum signal stability, and can be used in detection and quantitative analysis of low content compound, particularly thymine and the structure thereof similar to compound.
Description
Technical field
The present invention relates to the laser raman field, biochemical analysis detection range, a kind of specifically method of utilizing sodium polyacrylate to improve the Surface enhanced raman spectroscopy substrate.
Background technology
Nineteen twenty-eight, India physicist Raman (C.V.Raman) has at first been found the phenomenon that the frequency of monochromatic light diffusing coloured light after seeing through phenixin liquid changes, and afterwards, people are referred to as Ramam effect to this phenomenon.1974, the Raman signal that the pyridine that people such as Fleischman discovery is adsorbed on the silver electrode rough surface can be enhanced.The reason that signal strengthens is not only the increase that makes the pyridine Raman signal owing to the surface area increase of rough surface, but also owing to have certain new physics, chemical action in coarse silver electrode surface, this unusual Raman scattering strengthens phenomenon and is called as Surface enhanced raman spectroscopy (surface enhanced Raman scattering, SERS) effect.
The effect of Surface enhanced raman spectroscopy spectrum and the relation of substrate are very close, and the quality of substrate fabrication directly affects the effect of Surface enhanced raman spectroscopy spectrum.The method for making of Surface enhanced raman spectroscopy spectrum substrate has a variety of, and silver sol is the most frequently used a kind of.Silver sol is a kind of metastable state system, can form the aggregation that is easy to sedimentation behind the adding analysans.Because the consistance of character such as the grain size of colloid, shape, surface topography is difficult to control in the starting condition, directly causes the aggregation extent of colloidal sol to be difficult to determine, causes the less stable of Raman signal, the Surface enhanced raman spectroscopy spectral signal changes thereupon.The instability of Surface enhanced raman spectroscopy spectral signal is to utilize Surface enhanced raman spectroscopy spectrum the low content compound to be carried out the main difficulty of quantitative test.
Summary of the invention
At the defective of prior art, the invention provides a kind of preparation method of Surface enhanced raman spectroscopy substrate, adopt the substrate excellent stability of method preparation of the present invention, can be used for the low content compound is carried out quantitative test.
The present invention realizes by technical scheme once:
A kind of preparation method of Surface enhanced raman spectroscopy substrate is characterized in that, described method comprises the following steps:
1) silver nitrate between 45mg～65mg is added in the ultrapure water of 250ml, obtains liquor argenti nitratis ophthalmicus, and be heated to boiling,
2) being 0.5%～1% sodium citrate solution with mass concentration is added drop-wise in the liquor argenti nitratis ophthalmicus of step 1) with 10～15 droplets/minute speed, and the dropping time is 5 minutes, constantly stirs simultaneously, obtains silver sol,
3) sodium polyacrylate between 0.1g～1g is added in the ultrapure water of 100ml, obtains sodium polyacrylate solution,
4) with sodium polyacrylate solution and step 2) silver sol that obtains mixes, and stirs, and obtains the Surface enhanced raman spectroscopy substrate that makes detection signal stable.
Thymine, cytimidine, adenine, guanine are four bases that constitute DNA, are the base stocks that constitutes dna molecular, and important effect is arranged in the reproduction process of expression of gene and gene.Surface enhanced raman spectroscopy spectrum has remarkable advantages owing to have characteristics such as highly sensitive, that the water interference is little in the biochemical analysis context of detection.
Utilize the Surface enhanced raman spectroscopy substrate for preparing in the technique scheme, can carry out the detection of micro content thymine, detection method is as follows:
1, be 2 * 10 with concentration
-4Mol/L～1 * 10
-3The thymine of Mol/L mixes mutually with the pyridine of 0.1mol/L～0.5mol/L, obtains the mixed solution of thymine and pyridine,
2, thymine is mixed with substrate mutually with the mixed solution of pyridine, add the sodium chloride solution of 30～70mM simultaneously, vibration mixes solution,
3, the sample that makes is detected on Raman spectroscopy instrument.
Beneficial effect
Utilize the Surface enhanced raman spectroscopy substrate of preparation of the present invention, its spectral signal is highly stable, can detect and quantitative test the low content compound.Especially can detect thymine and similar cytimidine thereof, adenine, guanine.The present invention can make the Raman signal of thymine improve more than 20 times, and substrate was placed after 30 days, and the Raman signal of detection does not change.Concentration at thymine is 2 * 10
-4Mol/L～1 * 10
-3In the scope of Mol/L, presented good linear relationship between the analytical spectra peak of thymine and analogue thereof and pyridine the concentration, can be used for the quantitative test of sample as the ratio of interior mark spectral strength and thymine.
Description of drawings
Fig. 1 is the Raman figure (a) and 5 * 10 of the aqueous solution of 0.01mol/L
-4The Raman figure (b) of the thymine of mol/L in silver sol.
Fig. 2 is (a) and the Raman figure that places (b) after 30 days before thymine is placed in substrate of the present invention.
Fig. 3 is the Raman figure of thymine solution in substrate of the present invention that contains the internal standard compound pyridine.
Fig. 4 is that the concentration at thymine is 2 * 10
-4Mol/L～1 * 10
-3The linear relationship chart of realizing in the scope of Mol/L.
Embodiment
The invention will be further described below by instantiation.
Embodiment
The liquor argenti nitratis ophthalmicus (0.02%) of getting 100ml is in the beaker of 250ml, and the sodium citrate solution of 3ml (1%) is in graduated cylinder.Liquor argenti nitratis ophthalmicus is heated to boiling, under constantly stirring, sodium citrate solution is added wherein.Sodium citrate solution is added dropwise to complete, and fluidized state continued heated solution 10 minutes down; Stop heating, naturally cool to room temperature, obtain grizzly silver sol.
Get the silver sol of 20mL and the sodium polyacrylate of 20mL (0.5%) mixes, obtain the substrate that makes silver sol stable.The concentration of measuring 2mL respectively is 1mMol/L, 2mMol/L, 3mMol/L, 4mMol/L, the standard solution of the thymine of 5mMol/L, with the concentration of 2mL be that the pyridine solution of 0.1mol/L mixes, obtaining containing with pyridine is the thymine mixed solution of interior target variable concentrations.The thymine mixed solution of variable concentrations is added respectively in the volumetric flask of 10ml of the substrate that contains 4mL.The NaCl solution that further adds the 60mMol/L of 1mL, constant volume, at last with sample transfer in the sample bottle of measuring.
Sample is placed on the confocal laser micro-Raman spectroscopy (Britain Renishaw company) of Invia+Reflex.During measurement, adopting 50 double-lengths apart from object lens, is excitation source with the 514.5nm of Argon ion laser, and laser power is 20mw, carries out beam split with the 1800l/mm grating, and resolution is 1cm
-1, single pass, the time shutter is 10s.
In the Raman collection of illustrative plates to the sample of variable concentrations, all select for use with 783.4cm
-1Peak and 1035cm
-1The peak characteristic peak of representing the characteristic peak of thymine and pyridine as quantitatively peak and interior mark peak, with 783.4cm
-1Peak intensity and 1035cm
-1Peak intensity compare, be ordinate, be that horizontal ordinate is made linear relationship chart with concentration.
As can be seen from Figure 3, peak intensity and sample wire sexual intercourse are good, can satisfy the needs of quantitative test.In conjunction with Fig. 1 and Fig. 2 the substrate excellent stability that method of the present invention prepares is described, can be used for the low content compound is carried out quantitative test.
Claims (1)
1. the preparation method of a Surface enhanced raman spectroscopy substrate is characterized in that, described method comprises the following steps:
1) silver nitrate between 45mg～65mg is added in the ultrapure water of 250ml, obtains liquor argenti nitratis ophthalmicus, and be heated to boiling,
2) being 0.5%～1% sodium citrate solution with mass concentration is added drop-wise in the liquor argenti nitratis ophthalmicus of step 1) with 10～15 droplets/minute speed, and the dropping time is 5 minutes, constantly stirs simultaneously, obtains silver sol,
3) sodium polyacrylate between 0.1g～1g is added in the ultrapure water of 100ml, obtains sodium polyacrylate solution,
4) with the sodium polyacrylate solution and step 2 of step 3) gained) silver sol that obtains mixes, and stirs, and obtains the Surface enhanced raman spectroscopy substrate that makes detection signal stable.
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| CN2008100385367A CN101294904B (en) | 2008-06-05 | 2008-06-05 | Production method of surface reinforced Raman scattering substrate |
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| CN2008100385367A CN101294904B (en) | 2008-06-05 | 2008-06-05 | Production method of surface reinforced Raman scattering substrate |
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| CN101294904B true CN101294904B (en) | 2010-07-14 |
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| CN102269706A (en) * | 2011-06-13 | 2011-12-07 | 青岛农业大学 | Simple method for manufacturing plasma resonance controlled surface-enhanced Raman substrate |
| CN102269706B (en) * | 2011-06-13 | 2014-04-09 | 青岛农业大学 | Simple method for manufacturing plasma resonance controlled surface-enhanced Raman substrate |
| CN102998298A (en) * | 2012-12-13 | 2013-03-27 | 中山大学 | Method for rapidly detecting nitrite by using surface enhanced Raman spectrum and application thereof |
| CN102998298B (en) * | 2012-12-13 | 2016-02-03 | 中山大学 | Surface enhanced raman spectroscopy detects nitrite anions method and application thereof fast |
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