CN102391414A - Preparation method for temperature-sensitive surface enhanced Raman scattering probe - Google Patents
Preparation method for temperature-sensitive surface enhanced Raman scattering probe Download PDFInfo
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- CN102391414A CN102391414A CN2011102327796A CN201110232779A CN102391414A CN 102391414 A CN102391414 A CN 102391414A CN 2011102327796 A CN2011102327796 A CN 2011102327796A CN 201110232779 A CN201110232779 A CN 201110232779A CN 102391414 A CN102391414 A CN 102391414A
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Abstract
The invention discloses a preparation method for a temperature-sensitive surface enhanced Raman scattering (SERS) probe. The preparation method specifically comprises the following steps of: preparing temperature-sensitive polymer microspheres by taking N-isopropylacrylamide NIPAM as monomer, N,N-methylenebisacrylamide BIS as a crosslinking agent and 2,2'-azobis(isobutyramidine) dihydrochloride AAPH as an initiator by using a microemulsion polymerization method; then adding the temperature-sensitive polymer microspheres into mixed solution of hexadecyl trimethyl ammonium bromide surface modification agent and gold tetrachloride in a molar ratio of 10:1-100:1; reducing the gold tetrachloride by using sodium borohydride serving as a strong reducing agent to obtain a temperature-sensitive gold seed solution; preparing mixed solution of the hexadecyl trimethyl ammonium bromide, silver nitrate and the gold tetrachloride to obtain growth solution; and injecting the prepared temperature-sensitive gold seed solution into the growth solution, reacting for 3-4 hours, and adding organic molecules with SERS activity to obtain the temperature-sensitive surface enhanced Raman scattering (SERS) probe.
Description
Technical field:
The present invention relates to macromolecular material and field of nanometer material technology, be specifically related to a kind of preparation method with the temperature sensitive controlled hybridized nanometer microballoon of surface enhanced Raman scattering character.
Background technology:
In macromolecular material, the polymer/inorganic hybrid nano-material is because its many peculiar performances enjoy people's attention in recent years.Compound through with polymkeric substance; Inorganic nano-particle can be endowed many new characteristics; Like amphipathic, biological activity, chemically reactive, dispersibility, adsorptivity and organic phase capacitive etc., be worth and wide application prospect thereby show important use at aspects such as drug delivery, gene transfection, protein purifications.
Poly N-isopropyl acrylamide (PNIPAM) is a kind of polymkeric substance with temperature-responsive, and swelling is at high temperature shunk at low temperatures.It has a lowest critical solution temperature (LCST) about 32 ℃.When temperature during less than 32 ℃, PNIPAM shows wetting ability; When temperature during greater than 32 ℃, it shows hydrophobic nature.And the LCST of PNIPAM is adjustable in a big way, adds the hydrophilic polymerized monomer LSCT that can raise, and can reduce LCST otherwise add the hydrophobic nature comonomer.This special temperature-sensitive of PNIPAM makes it all obtain the extensive studies report in the controlled release field of drug delivery, temperature-sensitive switch and medicine.On the other hand, in recent years, metal nanoparticle relies on its excellent light, electricity, magnetic property also to obtain development rapidly, is bringing into play more and more important effect in fields such as photochemical catalysis, light sensing, medical science diagnosis and treatment.Therefore; Carry out PNIPAM and metal nanoparticle compound; The hybrid nano-material of preparing had both kept the temperature-sensing property of microballoon; Combined metal nanoparticle excellent optics and electrology characteristic again, can realize multi-functional integratedly, the intelligent material that has multiple response property for preparation is significant.
Surface enhanced Raman scattering technology (Surface enhanced Raman scattering, it is narrow SERS) to have a spectral line, and effectively the cancellation fluorescence background disturbs, and the finger print information of surveying sample can be provided, and sample is difficult for advantages such as photobleaching.Moreover, because the surface enhanced Raman scattering reinforcing effect (10 huge to Raman signal
5-10
6Doubly, even higher), make that the detectable level of sample can be very low even reach the unit molecule magnitude.The present favourable instrument that has become detection and analysis of biological samples based on the nanostructure and the nano-device of surface enhanced Raman scattering technology.
In sum, polymer P NIPAM is combined with metal nanoparticle, prepare hybrid nano-material, have great importance for the function and application field of expanding the SERS probe with temperature sensitive property and SERS characteristic double properties.
Summary of the invention
Technical problem:The object of the present invention is to provide a kind of system of temperature sensitive type surface-enhanced Raman scattering probe
Preparation Method, this method be the polymer microballoon of synthesized polymer monomer/PNIPAM nucleocapsid structure at first, and then at its surface in situ growth one deck gold nanorods, obtains the nano hybridization microballoon with SERS characteristic and temperature sensitive property dual nature.Through regulating the rising or the reduction of envrionment temperature, can realize that this nano hybridization microballoon SERS signal reversible strengthens or weakens, the application at aspects such as bio-sensing, drug controllable release has significant values for temperature sensing material.
Technical scheme:The preparation method of temperature sensitive type surface-enhanced Raman scattering probe of the present invention is specially:
1.) utilize the method for micro-emulsion polymerization, with N-NSC 11448 NIPAM as monomer, N; N-methylene-bisacrylamide BIS is as linking agent; 2,2'-azo diisobutyl amidine dihydrochloride AAPH is as causing Ji, at oxygen-free environment; Reacted 2 ~ 8 hours under 60 ~ 80 ℃ of water bath condition, prepare the temperature sensitive polymer microballoon;
2.) then this temperature sensitive polymer microballoon is joined in the mixing solutions of cetyl trimethylammonium bromide coating materials that mol ratio is 10:1 ~ 100:1 and tetra chlorauric acid; The hydrochloro-auric acid ion is adsorbed in the temperature sensitive polymer microballoon mesh through electrostatic adsorption, obtains temperature sensitive type gold seeds solution with strong reductant sodium borohydride reduction tetra chlorauric acid;
3.) the mixing solutions of preparation cetyl trimethylammonium bromide, Silver Nitrate and tetra chlorauric acid, three's mol ratio is 50:2:1 ~ 200:20:1, adds ascorbic acid solution then, obtains growth solution;
4.) the temperature sensitive type gold seeds solution of above-mentioned preparation is injected above-mentioned growth solution, react 3-4 hour, and adding has the active organic molecule of SERS, promptly obtain temperature sensitive type surface enhanced Raman scattering SERS probe.
The active organic molecule of the described SERS of having is the 4-Thiosalicylic acid, or 9-aminoacridine.
Described temperature sensitive type surface enhanced Raman scattering SERS probe, through regulating the temperature height of the probe aqueous solution, control surface strengthens the power of Raman scattering signal; When probe is placed in temperature < during 32 ℃ of aqueous solution; Because temperature sensitive polymer is in and unfolds state, gold nanorods distance to each other is bigger, the surface enhanced Raman scattering signal a little less than; When probe is placed in temperature>during 32 ℃ of aqueous solution; Temperature sensitive polymer shrinks, and the distance between the gold nanorods on surface diminishes, thereby causes the surface enhanced Raman scattering signal to strengthen.
Beneficial effect:
1, prepared SERS has SERS characteristic and temperature sensitive property double-response character simultaneously.Promptly along with the rising or the reduction of envrionment temperature, the strength of signal of SERS probe is reversible and strengthens or weaken.
2, since the present invention adopt the good polymer P NIPAM of bio-compatibility as temperature sensitive property material, utilize the method for growth in situ to prepare gold nanorods, the SERS probe that is obtained is nontoxic or toxicity is very little, but and in aqueous environments stable dispersion.
3, the SERS probe for preparing has particle diameter and sphere very uniformly, can be easy to regulate its size through changing synthesis condition.
4, the preparation method is simple, does not need special devices, operation at normal temperatures and pressures, and controllability is strong, good reproducibility.
Description of drawings:
Fig. 1 is the UV, visible light absorption spectrum of the temperature sensitive type SERS probe of the embodiment of the invention 1 preparation;
Fig. 2 is the temperature sensitive characteristic curve diagram of the temperature sensitive type SERS probe of the embodiment of the invention 1 preparation;
Fig. 3 is the surface enhanced Raman scattering collection of illustrative plates of temperature sensitive type SERS probe when high temperature and low temperature of the embodiment of the invention 1 preparation.
Embodiment
The technical process of the preparation of temperature sensitive type SERS probe of the present invention is: utilize the method for micro-emulsion polymerization, with N-NSC 11448 (NIPAM) as monomer, N; N-methylene-bisacrylamide (BIS) is as linking agent; 2,2'-azo diisobutyl amidine dihydrochloride (AAPH) is as causing Ji, at oxygen-free environment; Reaction is about 4 hours under 76 ℃ of water bath condition, prepares the temperature sensitive polymer microballoon; Then this temperature sensitive polymer microballoon is joined in the mixing solutions that contains a certain amount of cetyl trimethylammonium bromide coating materials and tetra chlorauric acid; The hydrochloro-auric acid ion is adsorbed onto in the temperature sensitive microballoon mesh through the electrostatic adsorption meeting, obtains temperature sensitive type gold seeds solution with strong reductant sodium borohydride reduction tetra chlorauric acid; The mixing solutions of preparation cetyl trimethylammonium bromide tetra chlorauric acid and Silver Nitrate adds ascorbic acid solution, obtains growth solution; A certain amount of seed solution is injected growth solution, reacted 3-4 hour, and add the SERS affinity tag, promptly obtain temperature sensitive type SERS probe.
Described temperature sensitive type SERS probe is characterized in that through attemperation size, can control surface strengthens the power of Raman scattering signal.During low temperature, because temperature sensitive polymer is in and unfolds state, gold nanorods distance to each other is bigger; The surface enhanced Raman scattering signal a little less than, when temperature raise, temperature sensitive polymer shrank; Distance between the gold nanorods on surface diminishes, thereby causes the surface enhanced Raman scattering signal to strengthen.
Below illustrate embodiment of the present invention, but content of the present invention is not limited to the example takeed.
Embodiment one
1) preparation of temperature sensitive polymer microballoon:
80 mg NIPAM and 5mg BIS are made into the 20 ml aqueous solution, and magnetic stirs, and logical argon gas is after half a hour; Add 1 ml (0.3 M) the AAPH aqueous solution, in reaction under 76 ℃ of water bath condition about 4 hours, eccentric cleaning; Again be distributed in the 10 ml deionized waters, obtain the temperature sensitive polymer microballoon.
2) preparation of temperature sensitive type gold seeds solution:
Under the stirring at room condition; In cetyl trimethylammonium bromide that concentration at 10mL is
and the mixing solutions of
tetra chlorauric acid; Add the above-mentioned temperature sensitive microballoon of 2ml; After magnetic stirs half a hour; Add abundant refrigerative
solution 2 ml in
ice-water bath rapidly; Vigorous stirring stops after 2 minutes stirring, and obtains temperature sensitive type gold seeds solution after the reaction.
3) preparation of growth solution:
The mixed solution of preparation 10ml cetyl trimethylammonium bromide, tetra chlorauric acid and Silver Nitrate in clean reactor drum; Wherein the cetyl trimethylammonium bromide volumetric molar concentration is
; The volumetric molar concentration of tetra chlorauric acid is
; The Silver Nitrate volumetric molar concentration is
; The mol ratio of Silver Nitrate and tetra chlorauric acid is 5:1; Place 28 ℃ water-bath to add 0.5ml (0.2M) ascorbic acid solution mixing solutions at last; Stir; Solution becomes colorless from orange-yellow, promptly obtains growth solution.
4) preparation of temperature sensitive type SERS probe:
In above-mentioned steps 3) in add 1ml in step 2 in the growth solution of configuration) in the temperature sensitive type seed solution that made, making the plain mol ratio of gold dollar of seed solution and growth solution is 10:3, gold nanorods promptly begins to grow.Add the growth solution behind the seed solution and under 28 ℃ water-bath, reacted 4 hours, added the spirituous solution (10 of SERS affinity tag 9-aminoacridine (9AA) then
-3~ 10
-8 
), promptly get temperature sensitive type SERS probe.
The UV, visible light absorption spectrum of this temperature sensitive type SERS probe is seen Fig. 1, and is visible by Fig. 1, and vertical plasma absorption peak of this temperature sensitive type SERS probe is near 760nm, and laterally the plasma peak is about 530nm.Gold nanorods more than 95% all is grown in temperature sensitive polymer microsphere surface Fig. 2, and the mean sizes of SERS probe is at 250nm under the room temperature.The mean sizes of this temperature sensitive type SERS probe raises along with temperature and diminishes, and phase transition temperature is about 32 ℃.When as can be seen from Figure 3 the SERS signal that when high temperature, records of this probe obviously is better than low temperature, explain that the temperature sensitive type SERS probe of preparation can strengthen the power of Raman scattering signal through the temperature variation control surface.
Embodiment two
1) preparation of temperature sensitive polymer microballoon:
200 mg NIPAM and 5mg BIS are made into the 20 ml aqueous solution, and magnetic stirs, and logical argon gas is after half a hour; Add 1 ml (0.3 M) the AAPH aqueous solution, in reaction under 76 ℃ of water bath condition about 4 hours, eccentric cleaning; Again be distributed in the 10 ml deionized waters, obtain the temperature sensitive polymer microballoon.
2) preparation of temperature sensitive type gold seeds solution:
Under the stirring at room condition; In cetyl trimethylammonium bromide that concentration at 10mL is
and the mixing solutions of
tetra chlorauric acid; Add the above-mentioned temperature sensitive microballoon of 2ml; After magnetic stirs half a hour; Add abundant refrigerative
solution 2 ml in
ice-water bath rapidly; Vigorous stirring stops after 2 minutes stirring, and obtains temperature sensitive type gold seeds solution after the reaction.
3) preparation of growth solution:
The mixed solution of preparation 10ml cetyl trimethylammonium bromide, tetra chlorauric acid and Silver Nitrate in clean reactor drum; Wherein the cetyl trimethylammonium bromide volumetric molar concentration is
; The volumetric molar concentration of tetra chlorauric acid is
; The Silver Nitrate volumetric molar concentration is
; The mol ratio of Silver Nitrate and tetra chlorauric acid is 40:3; Place 28 ℃ water-bath to add 0.5ml (0.2M) ascorbic acid solution mixing solutions at last; Stir; Solution becomes colorless from orange-yellow, promptly obtains growth solution.
4) preparation of temperature sensitive type SERS probe:
In above-mentioned steps 3) in add 1ml in step 2 in the growth solution of configuration) in the temperature sensitive type seed solution that made, making the plain mol ratio of gold dollar of seed solution and growth solution is 8:3, gold nanorods promptly begins to grow.Add the growth solution behind the seed solution and under 28 ℃ water-bath, reacted 4 hours, added the spirituous solution (10 of SERS affinity tag 4-Thiosalicylic acid then
-3~ 10
-8 
), obtaining temperature sensitive type SERS probe, the median size under its room temperature is of a size of 350 nm.
The above only is a preferred implementation of the present invention; Be noted that for those skilled in the art; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (3)
1. the preparation method of a temperature sensitive type surface-enhanced Raman scattering probe is characterized in that this preparation method is specially:
1.) utilize the method for micro-emulsion polymerization, with N-NSC 11448 NIPAM as monomer, N; N-methylene-bisacrylamide BIS is as linking agent; 2,2'-azo diisobutyl amidine dihydrochloride AAPH is as causing Ji, at oxygen-free environment; Reacted 2 ~ 8 hours under 60 ~ 80 ℃ of water bath condition, prepare the temperature sensitive polymer microballoon;
2.) then this temperature sensitive polymer microballoon is joined in the mixing solutions of cetyl trimethylammonium bromide coating materials that mol ratio is 10:1 ~ 100:1 and tetra chlorauric acid; The hydrochloro-auric acid ion is adsorbed in the temperature sensitive polymer microballoon mesh through electrostatic adsorption, obtains temperature sensitive type gold seeds solution with strong reductant sodium borohydride reduction tetra chlorauric acid;
3.) the mixing solutions of preparation cetyl trimethylammonium bromide, Silver Nitrate and tetra chlorauric acid, three's mol ratio is 50:2:1 ~ 200:20:1, adds ascorbic acid solution then, obtains growth solution;
4.) the temperature sensitive type gold seeds solution of above-mentioned preparation is injected above-mentioned growth solution, react 3-4 hour, and adding has the active organic molecule of SERS, promptly obtain temperature sensitive type surface enhanced Raman scattering SERS probe.
2. the preparation method of temperature sensitive type surface-enhanced Raman scattering probe according to claim 1 is characterized in that the active organic molecule of the described SERS of having is the 4-Thiosalicylic acid, or 9-aminoacridine.
3. the preparation method of temperature sensitive type surface-enhanced Raman scattering probe according to claim 1; It is characterized in that described temperature sensitive type surface enhanced Raman scattering SERS probe; Through regulating the temperature height of the probe aqueous solution, control surface strengthens the power of Raman scattering signal; When probe is placed in temperature < during 32 ℃ of aqueous solution; Because temperature sensitive polymer is in and unfolds state, gold nanorods distance to each other is bigger, the surface enhanced Raman scattering signal a little less than; When probe is placed in temperature>during 32 ℃ of aqueous solution; Temperature sensitive polymer shrinks, and the distance between the gold nanorods on surface diminishes, thereby causes the surface enhanced Raman scattering signal to strengthen.
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Cited By (6)
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| CN102706866A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof |
| CN103417191A (en) * | 2012-05-15 | 2013-12-04 | 南通大学 | Multifunctional Raman probe with detection, hyperthermia and chemotherapy properties |
| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
| CN110455777A (en) * | 2019-09-12 | 2019-11-15 | 中科院合肥技术创新工程院 | Creatinine detection method in Novel urine based on Surface enhanced Raman spectroscopy |
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN116698816A (en) * | 2023-05-06 | 2023-09-05 | 南通大学 | Preparation method and application of gold-loaded nanorod-hydrogel SERS sensor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103417191A (en) * | 2012-05-15 | 2013-12-04 | 南通大学 | Multifunctional Raman probe with detection, hyperthermia and chemotherapy properties |
| CN102706866A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof |
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| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
| CN110317294B (en) * | 2018-03-30 | 2021-06-18 | 长春理工大学 | Triphenylamine temperature-sensitive fluorescent polymer and preparation method thereof |
| CN110455777A (en) * | 2019-09-12 | 2019-11-15 | 中科院合肥技术创新工程院 | Creatinine detection method in Novel urine based on Surface enhanced Raman spectroscopy |
| CN110927141A (en) * | 2019-12-02 | 2020-03-27 | 辽宁大学 | Temperature-sensitive intelligent response SERS substrate and preparation method and application thereof |
| CN116698816A (en) * | 2023-05-06 | 2023-09-05 | 南通大学 | Preparation method and application of gold-loaded nanorod-hydrogel SERS sensor |
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