CN105755463A - Method for preparing hydrophobic surface solid monolayer uniform SERS substrate - Google Patents
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Abstract
The present invention discloses a method for preparing a hydrophobic surface solid monolayer uniform SERS substrate. The method comprises the steps of: preparing uniform metal nanoparticles and uniformly deposing monolayer metal nanoparticles on the surface of a hydrophobic material. The preparation of uniform metal nanoparticles includes: preparing a metal nano particle seed solution; rapidly transferring the prepared metal nanoparticle seed solution into a growing environment for uniform growth; and conducting low-speed centrifugation, and selecting spherical particles precipitated in the bottom of a centrifugal tube. The deposition of the monolayer metal nanoparticles specifically includes: calculating the amount of metal nanoparticles required for the deposition of the monolayer SERS substrate according to metal nanoparticle size; placing the hydrophobic material in the appropriate size subjected to silylation treatment in the bottom of a container; adding metal nanoparticle colloids; and drying the solvent to complete the preparation of solid monolayer uniform SERS substrate. The method can prepare metal nanoparticles with high uniformity and SERS substrate in tight monolayer arrangement, and greatly improves the uniformity of the monolayer SERS substrate prepared on the surface of the hydrophobic material.
Description
Technical field
The invention belongs to measurement, test or detection technique field, the preparation method of especially a kind of uniform SERS substrate of hydrophobic surface solid phase monolayer.
Background technology
Surface enhanced raman spectroscopy (SERS) has significantly high detection sensitivity, has broad application prospects in biomedicine, environmental monitoring, food safety and other industry, agricultural and scientific research.But this technology one serious deficiency of existence is exactly the lack of homogeneity of SERS substrate fabrication, particularly is difficult to form the uniform SERS substrate of larger area at hydrophobic surface, causes the poor repeatability of experiment, and reliability is not high, it is difficult to carry out detection by quantitative.
Accordingly, it would be desirable to it is carried out further research and improves.
Summary of the invention
Goal of the invention: the preparation method providing a kind of uniform SERS substrate of hydrophobic surface solid phase monolayer, to solve the problems referred to above that prior art exists.
Technical scheme: the preparation method of a kind of uniform SERS substrate of hydrophobic surface solid phase monolayer, including processing step as follows:
Step 1, prepare homogeneous metal nano-particle
Step 11, under the acid-base value of predetermined nucleation, prepare the metal nanoparticle seed solution that pattern is homogeneous, in this step, improved the uniformity of metal nanoparticle size by the precision of control ph；
Step 12, metal nanoparticle seed solution is transferred to growing environment, regulate pH value so that it is unanimously grow to design size, in this step, by regulating the size of the size adjustment metal nanoparticle of pH value；
Step 13, low-speed centrifugal several times, choose the spheroidal particle being deposited in bottom centrifuge tube, to improve metal nanoparticle uniformity further；
Step 2, at hydrophobic material surface uniform deposition single-layer metal nano-particle
Step 21, according to the metal nanoparticle size obtained, calculate the amount of metal nanoparticle needed for deposition monolayer SERS substrate；
Step 22, the hydrophobic material after the silanization treatment of suitable size is placed in container bottom, adds the metal nanoparticle colloid calculated, rapid dry out solvent, complete the uniform SERS substrate of solid phase monolayer and prepare.Suitable size refers to that material is adaptive with container, it is possible to be stuck in the bottom of container.
In a further embodiment: in described step 11, predetermined nucleation acid-base value refers to pH=11 ± 0.5, and metal nanoparticle can be made to grow to 65 ± 15 nanometers；It is preferably pH=11 ± 0.2, metal nanoparticle can be made to grow to 65 ± 5 nanometers；More preferably pH=11, can make metal nanoparticle grow to 65 ± 0.5 nanometers.Along with the accurate control of nucleation pH value, the size inhomogeneities of prepared metal nanoparticle can be made to be remarkably decreased.
In step 12, regulating pH value to 3.5, metal nanoparticle grows to 75 ± 0.5 nanometers；Regulating pH value to 4.5, metal nanoparticle grows to 65 ± 0.5 nanometers；Regulating pH value to 5.5, metal nanoparticle grows to 55 ± 0.5 nanometers.By the pH value in growth regulation stage, the metal nanoparticle of preparation can be made to grow to design size.
In step 13, centrifugal 4～8 times, rotating speed is 2200～2700 revs/min, and centrifugation time is 35～45 minutes, it is preferred to centrifugal 6 times, rotating speed is 2500 revs/min, and the time is 40 minutes.
In a further embodiment, described metal nanoparticle includes gold nano grain and silver nano-grain.
A kind of preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer, including processing step as follows:
Step 1: prepare uniform metal nanoparticle colloid:
Step 11, taking 0.5418g sodium citrate and be dissolved in the water of 4ml, regulating pH value is 11, is placed among boiling water and preheats, and is placed in ultrasonic machine supersound process；The silver nitrate taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and preheats；Prepared silver nitrate aqueous solution is injected in the sodium citrate solution that pH value is 11, after solution is creamy white, it is thus achieved that seed solution；
Step 12, the water taking 295ml are placed in three mouthfuls of round-bottomed flasks, and regulating its pH value is 4.5, oil bath heated and boiled, condensing reflux；The seed solution obtained in step 11 is rapidly injected in the aqueous solution that pH value is 4.5, after continuing maintenance heated and stirred 1.5h, natural cooling in stirring, complete silver nano-grain and prepare；
Step 13, prepared silver nano-grain is centrifuged, centrifugal speed 2500 revs/min, extracts the silver nano-grain being deposited in bottom centrifuge tube, after 6 times centrifugal, it is thus achieved that uniform, spherical silver nano-particle；
Step 2: prepare uniform monolayers film of metal nano-particles on hydrophobic material surface, specifically comprise the following steps that
After step 21, plasma cleaning PDMS substrate 40s, being placed on rapidly in the alcoholic solution of 5% (V/V) APTMS, temperature is 65 DEG C and keeps 6h, PDMS substrate is taken out, repeatedly rinses with dehydrated alcohol, remove unnecessary APTMS；
Step 22, the PDMS after step 21 processes is cut into suitable size, it is placed at the bottom of beaker, goes out the amount of the elargol needed at the bottom of densely covered beaker according to prepared silver nano-grain Size calculation, and be added in beaker, 50 DEG C of dry out solvent, complete uniform SERS substrate and prepare；
Step 23, with rhodamine 6G for probe molecule in prepared SERS substrate optional 10 do SERS detection, test result shows that the relative standard deviation of the uniform SERS substrate of solid phase monolayer that hydrophobic material PDMS surface prepares is only 11 ± 0.5%.
Beneficial effect: the present invention can prepare the significantly high metal nanoparticle of uniformity and the SERS substrate of tight monolayers arrangement, the relative standard deviation of metal nanoparticle is up to 7%, the relative standard deviation of SERS substrate is up to 11%, and the present invention substantially increases the uniformity preparing monolayer SERS substrate on hydrophobic material surface.
Accompanying drawing explanation
Silver nano-grain transmission electron microscope picture (TEM) and particle size distribution that Fig. 1 a and Fig. 1 b respectively prepares are added up.
The scanning electron microscope (SEM) photograph (SEM) of the SERS substrate that Fig. 2 PDMS is prepared on surface.
Fig. 3 a and Fig. 3 b respectively SERS spectrum and homogeneity statistical.
Fig. 4: have pH value regulation and control and the Spectral Extinction of the elargol without pH value regulation and control preparation.
Fig. 5: nucleation stage pH value is 11, the Spectral Extinction of growth stage pH value respectively 7.4 and 4.5 elargol prepared.
Fig. 6: growth stage pH value is 4.5, the Spectral Extinction of nucleation stage pH value respectively 12,11,9.7 and 8.7 elargol prepared.
Fig. 7 a to Fig. 7 f is respectively centrifuged the transmission electron microscope picture (TEM) of elargol after 0,4,6 times and the frequency statistics about silver nano-grain diameter of correspondence.
Fig. 8 a and Fig. 8 b respectively quantitative solvent evaporation and self-assembly method prepare the scanning electron microscope (SEM) photograph (SEM) of SERS substrate.
Detailed description of the invention
In order to solve the problems referred to above that prior art exists, applicant carried out and be deeply rich in and creatively study.It is found by the applicant that: SERS substrate uniformity is poor, and to be firstly because difficulty prepared by uniform metal nanoparticle relatively big, especially uniform silver nano-grain.And the uniform noble metal nano particles of pattern prepared by existing many chemical methodes is all by wrapping up one layer of other material or controlling its particular growth by adding surfactant, these all can greatly affect SERS application in later stage.Additionally, the difficulty being adsorbed onto equably by granule in hydrophobic substrate is also relatively larger, and due to the electrostatic repulsion between metallic particles, granule is difficult to tighten solid matter cloth in substrate.
For this, applicant proposed following scheme:
The preparation method of the currently preferred uniform SERS substrate of hydrophobic surface solid phase monolayer, including following two steps:
The first step: prepare uniform metal nanoparticle colloid, specifically include following steps:
A) taking 0.5418g sodium citrate and be dissolved in the water of 4ml, regulating its pH value is 11, is placed among boiling water and preheats, and is placed on inside ultrasonic machine ultrasonic；The silver nitrate taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and preheats；Prepared silver nitrate aqueous solution is injected in the sodium citrate solution that pH value is 11, after solution is creamy white, it is thus achieved that seed solution；
B) water taking 295ml is placed in three mouthfuls of round-bottomed flasks, and regulating its pH value is 4.5, oil bath heated and boiled, condensing reflux；The seed solution obtained in step A is rapidly injected in the aqueous solution that pH value is 4.5, after continuing maintenance heated and stirred 1.5h, natural cooling in stirring, complete silver nano-grain and prepare；
C) prepared silver nano-grain is repeatedly centrifuged, centrifugal speed 2500 revs/min, extract the silver nano-grain being deposited in bottom centrifuge tube, after 6 times centrifugal, obtain about 65nm, uniform, spherical silver nano-particle, relative standard deviation is only about 7%, as shown in accompanying drawing 1a and Fig. 1 b.
Second step: prepare uniform monolayers film of metal nano-particles on hydrophobic material (PDMS) surface, specifically comprise the following steps that
A) after plasma cleaning PDMS substrate 40s, being placed on rapidly 5% (V/V) APTMS alcoholic solution, temperature is 65 DEG C and keeps 6h, PDMS substrate is taken out, repeatedly rinses with dehydrated alcohol, remove unnecessary APTMS；
B) PDMS after processing of step A is cut into the size just can being stuck at the bottom of beaker, it is placed at the bottom of beaker, according to the silver nano-grain size prepared in the first step, calculate the amount of the elargol needed at the bottom of densely covered beaker, and it is added in beaker, 50 DEG C of dry out solvent, complete uniform SERS substrate and prepare, as shown in Figure 2.
C) with rhodamine 6G for probe molecule in prepared SERS substrate optional 10 be SERS detection, test result shows that the relative standard deviation of the uniform SERS substrate of solid phase monolayer that hydrophobic material PDMS surface prepares is only about 11%, as shown in accompanying drawing 3a and Fig. 3 b.
Example one:
The silver nitrate taking 0.051g is dissolved in the water of 5ml and obtains silver nitrate solution；Take 0.5418g sodium citrate and be placed in three mouthfuls of round-bottomed flasks, add the deionized water of 295ml, oil bath heated and boiled, stir energetically, condensing reflux.Adding silver nitrate solution after boiling, continue to keep heated and stirred 1.5h, flame-out, natural cooling in stirring, then prepared by elargol.The Spectral Extinction of the elargol of preparation as shown in Figure 4, absorbs peak position at about 413nm, halfwidth about 95nm.
And the Spectral Extinction of the elargol of preparation in above-mentioned preferred method, absorb peak position at about 415nm, halfwidth about 78nm.Owing to the peak position of Spectral Extinction is determined by the size of granule, and halfwidth is determined by the uniformity of granule, thus have the silver nano-grain of pH value regulation and control preparation than the silver nano-grain without pH value regulation and control preparation dimensionally greatly, good in uniformity.
Example two:
Taking 0.5418g sodium citrate and be dissolved in the water of 4ml, add a certain amount of sodium hydroxide solution, regulating its pH value is 11, is placed among boiling water and preheats, and is placed on inside ultrasonic machine ultrasonic；The silver nitrate taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and preheats.With needle tubing, silver nitrate solution is injected among sodium citrate solution, after solution is creamy white, the seed solution obtained is taken out inside ultrasonic machine；The water taking 295ml is placed in three mouthfuls of round-bottomed flasks, and oil bath heated and boiled stirs, condensing reflux energetically, after solution boiling, it is rapidly injected in flask by disposable for the silver-colored seed solution needle tubing obtained, after continuing maintenance heated and stirred 1.5h, flame-out, natural cooling in stirring, then prepared by elargol.The Spectral Extinction of the elargol of preparation is as it is shown in figure 5, absorb peak position at about 405nm.
And the Spectral Extinction of the elargol of preparation in above-mentioned method for optimizing, absorb peak position at about 415nm.Owing to the peak position of Spectral Extinction is determined by the size of granule, so the pH value (pH=4.5) in growth stage regulates and controls to make the size of granule bigger.
Example three:
Take 0.5418g sodium citrate and be dissolved in the water of 4ml, add a certain amount of sodium hydroxide solution, regulate its pH value respectively 12,11,9.7,8.7, be placed among boiling water and preheat, and be placed on inside ultrasonic machine ultrasonic；The silver nitrate taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and preheats.With needle tubing, silver nitrate solution is injected among sodium citrate solution, after solution is creamy white, the seed solution obtained is taken out inside ultrasonic machine；The water taking 295ml is placed in three mouthfuls of round-bottomed flasks, adding a certain amount of salpeter solution, regulating its pH value is 4.5, oil bath heated and boiled, stir energetically, condensing reflux, after solution boiling, is rapidly injected in flask by disposable for the silver-colored seed solution needle tubing obtained, after continuing maintenance heated and stirred 1.5h, flame-out, natural cooling in stirring, then prepared by elargol.The Spectral Extinction of the elargol of preparation is as shown in Figure 6, nucleation stage pH value is 12,11,9.7,8.7, growth stage pH value is all 4.5, absworption peak respectively 416nm, 415nm, 415nm, 416nm of corresponding elargol, but halfwidth respectively 92nm, 78nm, 97nm, 126nm.Owing to the peak position of Spectral Extinction is determined by the size of granule, and halfwidth is determined by the uniformity of granule, so the adjoining dimensions of these four silver nano-grain, and uniformity during nucleation stage pH=11 is best.
Example four:
The elargol that repeatedly low-speed centrifugal prepares, centrifugal speed 2500 turns, centrifugation time is 40min, directly reaches the bottom of centrifuge tube with dropper every time, draws the silver nano-grain being deposited in bottom.
Fig. 7 a and TEM that Fig. 7 b is the elargol directly prepared figure and the statistical distribution to silver nano-grain diameter, shown in Fig. 7 b, the average-size of Argent grain is between 60-70nm, and relative standard deviation is 13.31%.
Fig. 7 c and Fig. 7 d is that the method has been centrifuged the TEM figure of the elargol after 4 times and the statistical distribution to silver nano-grain diameter, and shown in Fig. 7 d, the average-size of Argent grain is between 60-65nm, and relative standard deviation is 10.40%.
Fig. 7 e and Fig. 7 f is that the method has been centrifuged the TEM figure of the elargol after 6 times and the statistical distribution to silver nano-grain diameter, and shown in Fig. 7 f, the average-size of Argent grain is at about 65nm, and relative standard deviation is 7.8%.Additionally, along with the increase of centrifugal number of times, bar-shaped silver nano-grain from the beginning account for the 2.18% of total particle, after centrifugal 6 times, bar-shaped silver nano-grain accounts for the 0.29% of total particle.
Example five:
The PDMS having modified amino is immersed in fulmargin prepared by above-mentioned method for optimizing, soaked overnight, catch silver nano-grain by amino, the scanning electron microscope (SEM) photograph of the SERS substrate of preparation is as shown in Figure 8 b.Can be seen that and directly catch Argent grain by amino, due to the electrostatic repulsion between Argent grain, the spacing of granule can not accomplish densification.And the SERS substrate of preparation just can accomplish the grain spacing of densification in method for optimizing, as shown in Figure 8 a.
From above-described embodiment:
Nucleation (seed solution) is separated by the present invention with growth course, is conducive to growing the uniform nano-particle with certain size.And the two process is not strictly separated by prior art, therefore, it is difficult to control the pH value of growth stage, the uniformity of the nano-particle of growth is also bad.The nano-particle only grown up to certain size just has good SERS activity.
Owing to PDMS is hydrophobic, the silver nano-grain being difficult in aqueous solution is combined, and present invention oxygen plasma+APTMS processes so that it is prone to be combined with silver nano-grain.
The present invention calculates the amount needed for monolayer alignment according to the particle size (Electronic Speculum result) grown, PDMS after processing is placed in container bottom, add the nano-particle calculated in container, rapid dry out solvent, complete the preparation of monolayer dense uniform SERS substrate.Method is simple, respond well.Adopting with prior art compared with the deposition nanometer particle film that is placed in fulmargin by PDMS self assembly, the effect of the present invention is substantially better.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple equivalents, these equivalents belong to protection scope of the present invention.
Claims (6)
1. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer, it is characterised in that include processing as follows step:
Step 1, prepare homogeneous metal nano-particle
Step 11, under the acid-base value of predetermined nucleation, prepare the metal nanoparticle seed solution that pattern is homogeneous, in this step, improved the uniformity of metal nanoparticle size by the precision of control ph；
Step 12, metal nanoparticle seed solution is transferred to growing environment, regulate pH value so that it is unanimously grow to design size, in this step, by regulating the size of the size adjustment metal nanoparticle of pH value；
Step 13, low-speed centrifugal several times, choose the spheroidal particle being deposited in bottom centrifuge tube, to improve metal nanoparticle uniformity further；
Step 2, at hydrophobic material surface uniform deposition single-layer metal nano-particle
Step 21, according to the metal nanoparticle size obtained, calculate the amount of metal nanoparticle needed for deposition monolayer SERS substrate；
Step 22, the hydrophobic material after the silanization treatment of suitable size is placed in container bottom, adds the metal nanoparticle colloid calculated in container, rapid dry out solvent, complete the uniform SERS substrate of solid phase monolayer and prepare.
2. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer as claimed in claim 1, it is characterised in that in described step 11, predetermined nucleation acid-base value refers to pH=11 ± 0.5, makes metal nanoparticle grow to 65 ± 15 nanometers；It is preferably pH=11 ± 0.2, metal nanoparticle can be made to grow to 65 ± 5 nanometers；More preferably pH=11, can make metal nanoparticle grow to 65 ± 0.5 nanometers.
3. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer as claimed in claim 1, it is characterised in that in step 12, regulates pH value to 3.5, and metal nanoparticle grows to 75 ± 0.5 nanometers；Or,
Regulating pH value to 4.5, metal nanoparticle grows to 65 ± 0.5 nanometers；Or,
Regulating pH value to 5.5, metal nanoparticle grows to 55 ± 0.5 nanometers.
4. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer as claimed in claim 1, it is characterised in that in step 13, centrifugal 4 ~ 8 times, rotating speed is 2200 ~ 2700 revs/min, and centrifugation time is 35 ~ 45 minutes, being preferably centrifugal 6 times, rotating speed is 2500 revs/min, and the time is 40 minutes.
5. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer as claimed in claim 1, it is characterised in that described metal nanoparticle is gold nano grain or silver nano-grain.
6. the preparation method of the uniform SERS substrate of hydrophobic surface solid phase monolayer, it is characterised in that include processing as follows step:
Step 1: prepare uniform metal nanoparticle colloid:
Step 11, taking 0.5418g sodium citrate and be dissolved in the water of 4ml, regulating pH value is 11, is placed among boiling water and preheats, and is placed in ultrasonic machine supersound process；The silver nitrate taking 0.051g is dissolved in the water of 1ml, is placed in boiling water and preheats；Prepared silver nitrate aqueous solution is injected in the sodium citrate solution that pH value is 11, after solution is creamy white, it is thus achieved that seed solution；
Step 12, the water taking 295ml are placed in three mouthfuls of round-bottomed flasks, and regulating its pH value is 4.5, oil bath heated and boiled, condensing reflux；The seed solution obtained in step 11 is rapidly injected in the aqueous solution that pH value is 4.5, after continuing maintenance heated and stirred 1.5h, natural cooling in stirring, complete silver nano-grain and prepare；
Step 13, prepared silver nano-grain is centrifuged, centrifugal speed 2500 revs/min, extracts the silver nano-grain being deposited in bottom centrifuge tube, after 6 times centrifugal, it is thus achieved that uniform, spherical silver nano-particle；
Step 2: prepare uniform monolayers film of metal nano-particles on hydrophobic material surface, specifically comprise the following steps that
After step 21, plasma cleaning PDMS substrate 40s, being placed on rapidly in the alcoholic solution of 5%APTMS, temperature is 65 DEG C and keeps 6h, PDMS substrate is taken out, repeatedly rinses with dehydrated alcohol, remove unnecessary APTMS；
Step 22, the PDMS after step 21 processes is cut into suitable size, it is placed at the bottom of beaker, goes out the amount of the elargol needed at the bottom of densely covered beaker according to prepared silver nano-grain Size calculation, and be added in beaker, 50 DEG C of dry out solvent, complete uniform SERS substrate and prepare；
Step 23, with rhodamine 6G for probe molecule in prepared SERS substrate optional 10 do SERS detection, test result shows that the relative standard deviation of the uniform SERS substrate of solid phase monolayer that hydrophobic material PDMS surface prepares is 11 ± 0.5%.
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| CN110511418A (en) * | 2019-07-11 | 2019-11-29 | 宁波大学 | Silver-colored nanowires of gold PDMS composite film material and its preparation method and application for SERS detection |
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| CN115582537A (en) * | 2022-10-08 | 2023-01-10 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106645087A (en) * | 2016-12-22 | 2017-05-10 | 东南大学 | PDMS-base single-layer SERS substrate not requiring surface modification and preparation method thereof |
| CN108226135A (en) * | 2018-01-26 | 2018-06-29 | 江南大学 | A kind of compound film sensors and its method for detecting vibrio parahemolyticus |
| CN108226135B (en) * | 2018-01-26 | 2020-12-29 | 江南大学 | Composite membrane sensor and method for detecting vibrio parahaemolyticus by using same |
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| CN110511418B (en) * | 2019-07-11 | 2021-10-29 | 宁波大学 | Silver-gold nanowire PDMS composite film material for SERS detection and preparation method and application thereof |
| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
| CN115582537A (en) * | 2022-10-08 | 2023-01-10 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
| CN115582537B (en) * | 2022-10-08 | 2023-05-16 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
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