CN106041125A - SiO2 gold nanorod composite particle preparation method - Google Patents

Abstract

The invention discloses a SiO2 gold nanorod (GNR) composite particle preparation method, which comprises the steps of preparing growth solution, preparing GNR, and preparing GNR-SiO2. The method disclosed by the invention achieves good repeatability, ideal near-infrared excitation window and ideal light-thermal conversion efficiency, and improves the application value of the GNR in the biological field.

Description

A kind of SiO2The preparation method of gold nanorods compound particle

Technical field

The present invention relates to material synthesis method, the preparation method of a kind of SiO2 gold nanorods compound particle.

Background technology

Owing to having the physicochemical property of uniqueness, golden nanometer particle always is the focus in nano materials research, Qi Zhongyou The most prominent with gold nanorods (GNR).Owing to the local surface plasma resonance (LSPR) of GNR has height The adjustability of degree, it can be ensured that its excite window to be in penetration into tissue is higher, cytotoxicity is less near infrared region.So, GNR has in histiocyte imaging field and is quite widely applied.Additionally, GNR can be the highest by photo-thermal effect Imitate converts light energy into heat energy.The heat energy produced is possible not only to be directly used in the thermal therapeutical of tumor cell, it is also possible to be used for touching Send out the release of nano-carrier Chinese medicine.

The preparation method of GNR is generally required for using the cetyl trimethylammonium bromide (CTA of high concentration B) stablizing of gold nanorods is maintained.But CTAB has a stronger bio-toxicity, and the depositing of CTAB bilayer molecules Directly effect is there is also making other molecules be difficult to GNR surface.After reducing the concentration of CTAB, GNR warp Often there will be particle accumulation, cause its local surface LSPR absworption peak that the most serious skew occurs；Remove surface completely After activating agent, GNR there will be irreversible particle accumulation and thoroughly loses its optical characteristics.And put down as medicine carrying Platform, the specific surface area of GNR is too small, seriously limits the useful load of medicine.GNR is carried out SiO2 embedding, it is not necessary to Stabilizer gets final product more stable dispersion.Meanwhile, SiO2 has excellent light transmission, to the GNR absorbing properties after cladding Affect less, also there is good biocompatibility, it is easy to carry out surface biological modification.

Summary of the invention

The technical problem to be solved is to provide the preparation method of a kind of SiO2 gold nanorods compound particle, carries For a kind of new synthetic method.

The synthetic method that the present invention uses, comprises the steps:

A, take the chlorauric acid solution of 103 μ L1mg/mL and the miscible conjunction of CTAB of 0.5mL 0.2 mol/L, will The 0.227mg/mLNaBH that 100 μ L newly join₄Solution, joins in above-mentioned solution, solution colour with vigorous stirring Being become brown color from yellow, stop, preparing crystal seed after stirring 2min, seed-solution need to keep 25min at 35 DEG C before using；

B, preparing growth-promoting media, 1.8gCTAB Yu 0.22g5-BrSA is placed in beaker with 95mL warm water (50-70 DEG C) Dissolving, silver nitrate (AgNO3) solution (0.004mol/L) and the 2.5mL hydrochloric acid that add 3.8mL in this solution backward are water-soluble Liquid (1mol/L), is cooled to solution 30 DEG C, is then added thereto by the chlorauric acid solution of 2.06mL 10mg/mL, mixed Closing liquid and keep 20min at 32 DEG C, be then added thereto to the ascorbic acid of 0.4mL 0.064 mol/L, solution acutely stirs Mix 30s until it becomes colorless, prepare growth-promoting media;

C, preparation GNR, the seed-solution taking 0.08mL adds in growth-promoting media, after mixed liquor stirring 30s at 30 DEG C static 12 H, removes supernatant after product 12000r/min is centrifuged 25min, and precipitate is redispersed in 25mL water, prepares GNR;

The preparation of d, GNR-SiO2, takes GNR dispersion liquid 10mL, adds 100 μ L sodium hydrate aqueous solution (1mol/L) by pH Value regulation is to 9.5, under then stirring at 35 DEG C, drips 2mL tetraethyl orthosilicate ethanol solution, each 200 μ L, interval 30min, after dropping, continues to stir 36h at 40 DEG C, and after completion of the reaction, 12000r/min is centrifuged 25min, precipitate salt Acid ethanol solution V(concentrated hydrochloric acid): V(ethanol)=1:8.5 ］ centrifuge washing 2 times, remove CTAB, after washing, product is divided Dissipate in 10mL water, prepare GNR-SiO2.

The invention has the beneficial effects as follows: preparation method favorable repeatability there is preferable near-infrared and excite window and photo-thermal Transformation efficiency, significantly improves the GNR using value at biological field.

Detailed description of the invention

Further illustrating present disclosure below in conjunction with example, as known by the technical knowledge, the present invention also can pass through other The scheme without departing from the technology of the present invention feature describe, the most all within the scope of the present invention or equivalent the scope of the invention in Change and be all included in the invention.

Embodiment:

Take the chlorauric acid solution of 103 μ L1mg/mL and the miscible conjunction of CTAB of 0.5mL 0.2 mol/L, by 100 μ The 0.227mg/mLNaBH that L newly joins₄Solution, joins in above-mentioned solution with vigorous stirring, and solution colour is by Huang Complexion changed is brown color, stops, preparing crystal seed after stirring 2min, and seed-solution need to keep 25min at 35 DEG C before using；

Preparing growth-promoting media, 1.8gCTAB with 0.22g5-BrSA is placed in beaker with 95mL warm water (50-70 DEG C) molten Solve, this solution backward adds silver nitrate (AgNO3) solution (0.004mol/L) and the 2.5mL aqueous hydrochloric acid solution of 3.8mL (1mol/L), solution is cooled to 30 DEG C, then the chlorauric acid solution of 2.06mL 10mg/mL is added thereto, mixing Liquid keeps 20min at 32 DEG C, is then added thereto to the ascorbic acid of 0.4mL 0.064 mol/L, and solution is stirred vigorously 30s, until it becomes colorless, prepares growth-promoting media;

Preparation GNR, the seed-solution taking 0.08mL adds in growth-promoting media, after mixed liquor stirring 30s at 30 DEG C static 12h, Removing supernatant after product 12000r/min is centrifuged 25min, precipitate is redispersed in 25mL water, prepares GNR;

The preparation of GNR-SiO2, takes GNR dispersion liquid 10mL, adds 100 μ L sodium hydrate aqueous solution (1mol/L) by pH value Regulation is to 9.5, under then stirring at 35 DEG C, drips 2mL tetraethyl orthosilicate ethanol solution, each 200 μ L, interval 30min, after dropping, continues to stir 36h at 40 DEG C, and after completion of the reaction, 12000r/min is centrifuged 25min, precipitate salt Acid ethanol solution V(concentrated hydrochloric acid): V(ethanol)=1:8.5 ］ centrifuge washing 2 times, remove CTAB, after washing, product is divided Dissipate in 10mL water, prepare GNR-SiO2.

The seeded growth method using silver ion mediation is prepared for the GNR of different LSPR absworption peak, and to LSPR Absworption peak is that the GNR of 800nm has carried out SiO2 embedding, is successfully prepared shell thickness and is respectively the GNR-SiO2 of 35nm, preparation Method has higher repeatability.The surface potential of GNR-SiO2 is inverted to nagative potential by positive potential, for-15.3mV, pole The earth improves the GNR using value at biological field.

By GNR-SiO2 morphosis, surface potential, optical characteristics and photothermal conversion effect having been carried out exterior syndrome, having divided Analysis and research.Result shows that optical characteristics, photothermal conversion and the heat radiation of GNR are had little to no effect by SiO2 embedding. GNR- SiO2 has preferable near-infrared and excites window and photothermal conversion efficiency.

Claims (1)

1. a preparation method for SiO2 gold nanorods compound particle, comprises the steps:

A, take the chlorauric acid solution of 103 μ L1mg/mL and the miscible conjunction of CTAB of 0.5mL 0.2 mol/L, will The 0.227mg/mLNaBH that 100 μ L newly join₄Solution, joins in above-mentioned solution with vigorous stirring, solution colour by Yellow becomes brown color, stops, preparing crystal seed after stirring 2min, and seed-solution need to keep 25min at 35 DEG C before using；

B, preparing growth-promoting media, 1.8gCTAB Yu 0.22g5-BrSA is placed in beaker with 95mL warm water (50-70 DEG C) Dissolving, silver nitrate (AgNO3) solution (0.004mol/L) and the 2.5mL hydrochloric acid that add 3.8mL in this solution backward are water-soluble Liquid (1mol/L), is cooled to solution 30 DEG C, is then added thereto by the chlorauric acid solution of 2.06mL 10mg/mL, mixed Closing liquid and keep 20min at 32 DEG C, be then added thereto to the ascorbic acid of 0.4mL 0.064 mol/L, solution acutely stirs Mix 30s until it becomes colorless, prepare growth-promoting media;

C, preparation GNR, the seed-solution taking 0.08mL adds in growth-promoting media, after mixed liquor stirring 30s at 30 DEG C static 12 H, removes supernatant after product 12000r/min is centrifuged 25min, and precipitate is redispersed in 25mL water, prepares GNR;

The preparation of d, GNR-SiO2, takes GNR dispersion liquid 10mL, adds 100 μ L sodium hydrate aqueous solution (1mol/L) by pH Value regulation is to 9.5, under then stirring at 35 DEG C, drips 2mL tetraethyl orthosilicate ethanol solution, each 200 μ L, interval 30min, after dropping, continues to stir 36h at 40 DEG C, and after completion of the reaction, 12000r/min is centrifuged 25min, precipitate salt Acid ethanol solution V(concentrated hydrochloric acid): V(ethanol)=1:8.5 ］ centrifuge washing 2 times, remove CTAB, after washing, product is divided Dissipate in 10mL water, prepare GNR-SiO2.