CN106141201B - A method of improving gold nanorods light thermal property and photo and thermal stability - Google Patents
A method of improving gold nanorods light thermal property and photo and thermal stability Download PDFInfo
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- CN106141201B CN106141201B CN201610740984.6A CN201610740984A CN106141201B CN 106141201 B CN106141201 B CN 106141201B CN 201610740984 A CN201610740984 A CN 201610740984A CN 106141201 B CN106141201 B CN 106141201B
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Abstract
The present invention provides a kind of gold nanorods of modification, the gold nanoclusters wrapped up by bovine serum albumin (BSA) are coated with, a kind of novel nano compound is constituted.This compound is exposed to light thermal property and stability under the irradiation of near infrared light for probing into it.After the near infrared light repeatedly recycled, for the optical property and pattern of gold nanoclusters gold nanorods compound there is no significant change, heating is significantly raised.As a comparison, identical gold nanorods and bovine serum albumin is successively used to wrap up gold nanorods as stability control experiment.In addition, the light thermal property and colloidal stability of gold nanoclusters gold nanorods compound have fabulous reproducibility.Therefore, it is this improve photo-thermal property, photo and thermal stability nano-complex be highly suitable for further biologic applications, such as remote sensing, bio-imaging and photo-thermal therapy.
Description
Technical field
The present invention relates to a kind of methods for improving gold nanorods photo and thermal stability.More particularly to by with bovine serum albumin packet
The electrostatic interaction for the gold nanoclusters wrapped up in is compound to improve the warm performance of gold nanorods, photo and thermal stability and biocompatibility
Method.
Background technique
Near infrared light refers to electromagnetic wave of the wavelength in the near infrared region in (780nm -2526nm).Relative to ultraviolet light and
For visible light, near-infrared laser irradiation can penetrate into deep layer subcutaneous tissue, and to the injury pole of the health tissues of surrounding
It is small.And many nano particles, such as copper sulphide nano crystalline substance, gold nanorods, Golden Triangle piece etc., all have in near-infrared wavelength area
Unique surface plasmon absorption.Based on this special optical property, near infrared light to these nano materials into
Certain heat can be generated after row irradiation.And pass through intensity, the concentration of irradiation duration, fluid sample for changing laser
Deng, thus it is possible to vary generate heat number, carry out quantitatively regulating and controlling.Therefore, the nano material with near-infrared absorption is as light
Thermit powder is just being extensively studied applied to drug release, cancer diagnosis and treatment, the fields such as sensor.
Gold nanoclusters (GNC, Gold Nanocluster), be a kind of combined by more than ten of atom to tens atoms and
At, nanoparticle of the diameter less than 2 nanometers.Since GNC is found, due to its lesser size and excellent fluorescence property and
Good biocompatibility has a wide range of applications in terms of tumour cell.The bovine serum albumin of its surface package
It (BSA) is a kind of common protein, it is cheap, simple and easy to get；But this does not interfere it wide in terms of biologic applications
Development prospect.The organism application aspect of the nanoparticle especially quickly grown in recent years, BSA are used to increase nanoparticle
The biocompatibility of son helps nanoparticle to carry out endocytosis exocytosis etc..
Gold nanorods (GNR) are as a photo-thermal therapy agent near infrared region region response, to cancer cell and tumour
Destructive power it is very significant, in terms of photo-thermal therapy have vast potential for future development.It is well known, however, that gold nano
Stick has biggish bio-toxicity due to cetyl trimethylammonium bromide (CTAB) duplicature on its surface.And GNR is being passed through
Deformation occurs for meeting when crossing laser emission, and photo-thermal effect reduces.These unfavorable factors limit its further application.
Due to gold nanorods (GNR) and bovine serum albumin (BSA) is compound can improve these nano materials and control in radiant heat
Performance and composite material in treatment have brilliant biocompatibility, so this research in the recent period receives a large amount of concern.
However there are no about the compound carry out green high-efficient of gold nanoclusters wrapped up by bovine serum albumin in currently available technology document
Gold nanorods it is surface modified and improve the report of its photo and thermal stability and biocompatibility successful case.
Summary of the invention
One object of the present invention is to provide a kind of method for improving gold nanorods light thermal property and photo and thermal stability,
It is able to solve gold nanorods as a near-infrared and responds optothermal material stability, the problem that light thermal property is not good enough.
One object of the present invention is to provide a kind of method for improving gold nanorods light thermal property and photo and thermal stability,
Its biocompatibility that can be improved the gold nanorods after modification.
One object of the present invention is to provide a kind of method for improving gold nanorods light thermal property and photo and thermal stability,
This method is convenient and reliable.
One object of the present invention is to provide a kind of method for improving gold nanorods light thermal property and photo and thermal stability,
With two or more in above-mentioned purpose.
One object of the present invention is to provide a kind of gold nanorods of modification, is able to solve gold nanorods as one
A near-infrared responds optothermal material stability, the problem that light thermal property is not good enough, and/or is able to solve the gold nano after modification
The biocompatibility of stick.
An aspect of of the present present invention provides a kind of method for improving gold nanorods light thermal property and photo and thermal stability, wherein gold
Nanometer rods are the gold nanorods composite nano materials that gold nanoclusters wrap up ascorbic acid or dopamine reduction, are included at least as follows
Step:
(1), gold nanorods (GNRs) solution is prepared；
(2), gold nanoclusters (GNC) solution of bovine serum albumin (BSA) package is prepared；
(3), gold nanoclusters gold nanorods composite material (GNC-GNRs) is prepared by electrostatic interaction.
In step (1), by gold nanorods milli-Q water, it is centrifuged off supernatant, and disperse again；
Preferably, gold nanorods are synthesized with golden kind of a growth method, use cetyl trimethylammonium bromide (CTAB) as
Stabilizer；
Preferably, when reducing agent is ascorbic acid prepared by gold nanorods solution with the following method: gold chloride
(HAuCl4) mixed well with the cetyl ammonium bromide (CTAB) of 5mL 0.2M, sequentially add the nitric acid that 200uL concentration is 4mM
Silver (AgNO3) solution, 70uL 100mM ascorbic acid (AA), be vigorously stirred, solution is become colorless by yellow, finally, be added
120uL gold kind of solution, is placed in 28 DEG C of water-baths after gently shaking up and reacts 12h, it is that gold nanorods are molten that solution, which becomes darkviolet,
Liquid；
Preferably, when reducing agent is dopamine (DA) prepared by gold nanorods solution with the following method: by HAuCl4With
9.50mL concentration is that the CTAB solution of 0.1M mixes well, and mixed liquor is placed on 40 DEG C of metal baths and stands 10min；Later successively
The AgNO that 70uL concentration is 0.1M is added3Solution, 500uL concentration are 40mg/mL brand-new dopamine (DA) solution, are shaken up, solution
Become light yellow from yellow, finally, golden kind of the solution of injection 160uL, reacts 3h in 42.5 DEG C of metal baths, solution becomes sepia i.e.
For gold nanorods solution；
Preferably, the concentration of the gold nanorods aqueous solution is 0.2nM；
Preferably, extra CTAB can be removed by centrifugation in the gold nanorods of synthesis；
Preferably, each centrifugation time is 9-11min, and centrifugation number is twice；It is furthermore preferred that centrifugation time is 9 every time
Minute, 10 minutes or 11 minutes；
Preferably, after being centrifuged twice, dispersed again using neutral ultrapure water；
Preferably, in step (2), by gold chloride (HAuCl4) be sufficiently mixed with BSA, after stirring, NaOH solution is added,
Continue to stir, reaction 12-15 hour after, solution be it is orange red, be placed in be irradiated in camera bellows with the light of 365nm and watch red
Fluorescence, that is, GNC synthesis finishes；
Preferably, the chlorauric acid solution concentration used is 10mM, volume 5mL；Bovine serum albumen solution concentration is 50mg/
ML, volume 50mL；
Preferably, reaction optimum temperature is 37 DEG C；
Preferably, the reaction time is 12 hours；
Preferably, the reaction time is 13 hours；
Preferably, the reaction time is 14 hours；
Preferably, the reaction time is 15 hours.
Preferably, in step (3), gold nanorods solution is placed in centrifuge tube, controlled at 36- on metal bath
38 DEG C, the gold nanoclusters solution of injection step (2) mixes；Water is added to make the volume 1mL of entire solution, static 20-45min
Gold nanoclusters are sufficiently reacted with gold nanorods；
Preferably, the concentration of gold nanorods solution is 0.2nM, volume 500uL；
Preferably, the volume of gold nanoclusters is 150uL-450uL；It is furthermore preferred that the volume of gold nanoclusters be 150uL,
200uL, 250uL, 300uL, 350uL, 400uL and 450uL；It is further preferred that the volume of gold nanoclusters is 300uL；
Preferably, reaction optimum temperature is 37 DEG C；
Preferably, quiescent time is 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes and 45 minutes；It is furthermore preferred that
Quiescent time is 30 minutes.
It further, further include step (4): purifying gold nanoclusters gold nanoparticle composite nanoparticle.
Preferably, it in step (4), is purified by the way of being centrifuged twice；
Preferably, being centrifuged revolution used is 8000-10000rpm；It is further preferred that the used revolution of centrifugation be 8000rpm,
9000rpm,10000rpm rpm；It is furthermore preferred that revolution used in centrifugation is 9000rpm；
Preferably, centrifugation time is 9-12 minutes, more preferable 9 minutes, 10 minutes, 11 minutes, 12 minutes, it is further preferred that from
The heart time is 10 minutes；
Preferably, composite nanoparticle after purification is divided equally and is scattered in ultrapure water；
Preferably, centrifugal rotational speed 10000rpm, time are 10 minutes.
Another aspect of the present invention is provided a kind of modified gold nanorods, is prepared using above method, is had good
Good light thermal property and stability.
Modified gold nanorods provided by the present invention, wherein the particle of the modification gold nanorods, the side of gold nanorods particle
Edge has BSA shell, and gold nanoclusters particle is distributed in BSA shell.Preferably, BSA shell thickness is greater than 2nm；Preferably,
BSA shell thickness is about 3nm；Preferably, the gold nanoclusters particle greater than 0.5nm is distributed in BSA shell；Preferably, exist
The gold nanoclusters particle of about 1nm is distributed in BSA shell.
Modified gold nanorods provided by the present invention, wherein use the composite modified gold nanorods solution that OD value is 0.8
The 808nm near-infrared continuous wave of 2.97W illumination 5 minutes, the data with following light thermal property: heating rate is more than 3.5 DEG C/
min；Preferably, heating rate is more than 4 DEG C/min；Preferably, heating rate is more than 4.5 DEG C/min.
Preferably, composite nanoparticle solution is after irradiation 5 minutes, the data with following photo and thermal stability: heating
Rate is no more than 12% decaying；It is undeformed in electron microscopic picture；Ultraviolet spectra is unchanged.
Method in the present invention mainly utilizes the electrostatic between the bovine serum albumin and gold nanorods on gold nanoclusters surface to make
With so that two kinds of nano material interactions be made to form new composite nano materials together.
By the formation mechenism of gold nanoclusters gold nanorods composite nanoparticle it can be concluded that by surface modified
Nanoparticle destroyed due to CTAB duplicature, so there is very outstanding biocompatibility, therefore the method is very big
The limitation for solving nano material and being applied in biological field.
Specifically, since the water solubility of gold nanoclusters shows as the gold nanorods modified through gold nanoclusters
Water solubility has good colloidal stability.
Not the deficiencies of light thermal property that the present invention reports before solving is not good enough, stability is poor, toxic.Using the present invention, have
Help further biomolecule modification and the application in biomedical aspect, such as remote sensing, bio-imaging and photo-thermal therapy.
Detailed description of the invention
Gold nanorods (GNRs), the gold nanorods (BSA- after BSA is modified of Fig. 1 ascorbic acid reduction preparation
GNRs the ultraviolet spectra of the gold nanorods (GNC-GNRs)) and after gold nanoclusters are modified.
Gold nanorods (GNRs) (A), the gold nanorods (BSA- after BSA is modified of Fig. 2 ascorbic acid reduction preparation
GNRs) the transmission electron microscope of (B) and the gold nanorods (GNC-GNRs) (C) after gold nanoclusters are modified.
Fig. 3 pure water (Pure water), gold nanoclusters (GNCs), ascorbic acid reduction preparation gold nanorods (GNRs),
Gold nanorods (BSA-GNRs) after BSA is modified and gold nanorods (GNC-GNRs) sample after gold nanoclusters are modified
Solution is in the average ramp case after 3 reirradiations (808nm, 2.97W).
Gold nanorods (GNRs) (A), the gold nanorods (BSA- after BSA is modified of Fig. 4 ascorbic acid reduction preparation
GNRs) (B) and gold nanorods (GNC-GNRs) (C) sample solution after gold nanoclusters are modified are in 3 reirradiations
The heating curve of (808nm, 2.97W).
Gold nanorods (GNRs), the gold nanorods (BSA- after BSA is modified of Fig. 5 ascorbic acid reduction preparation
GNRs gold nanorods (GNC-GNRs) sample solution) and after gold nanoclusters are modified by 3 reirradiations (808nm,
Transmission electron microscope photo after 2.97W).
Gold nanorods (GNRs), the gold nanorods (BSA-GNRs) after BSA is modified of Fig. 6 dopamine reduction preparation
With the ultraviolet spectra of the gold nanorods (GNC-GNRs) after gold nanoclusters are modified.
Gold nanorods (GNRs) (A), the gold nanorods (BSA- after BSA is modified of Fig. 7 dopamine reduction preparation
GNRs) the transmission electron microscope of (B) and the gold nanorods (GNC-GNRs) (C) after gold nanoclusters are modified.
Gold nanorods (GNRs), warp prepared by Fig. 8 pure water (Pure water), gold nanoclusters (GNCs), dopamine reduction
Gold nanorods (BSA-GNRs) after crossing BSA modification and gold nanorods (GNC-GNRs) sample after gold nanoclusters are modified are molten
Liquid is in the average ramp case after 3 reirradiations (808nm, 2.97W).
Fig. 9 dopamine reduction preparation gold nanorods (GNRs), after BSA is modified gold nanorods (BSA-GNRs) and
Gold nanorods (GNC-GNRs) after gold nanoclusters are modified are in the transmission after 3 reirradiations (808nm, 2.97W)
Electromicroscopic photograph.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art answer
It should be appreciated that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form repair
Change or replace, but these modifications and replacement are fallen within the protection scope of the present invention.
Preparation method in following embodiments is unless otherwise specified conventional method；Experimental material used, such as nothing
Specified otherwise is that conventional biochemical reagent manufacturer is commercially available.
Embodiment 1:
Prepare gold nanoclusters (GNC) solution wrapped up with bovine serum albumin(BSA) (BSA):
The HAuCl for being 10mM by 5mL concentration4It is sufficiently mixed with 5mL concentration for the BSA of 50mg/mL, is filled at 37 DEG C
Divide and stir, after 2min, rapidly joining 0.5mL concentration is 1M brand-new NaOH, and continuation is stirred at 37 DEG C, molten after reacting 12h
Liquid be it is orange red, be placed in camera bellows be irradiated with the light of 365nm watch red fluorescence i.e. GNC synthesis finish.
Embodiment 2:
Gold nanorods (GNRs) solution of ascorbic acid (AA) reduction is prepared with crystal seed growth method:
(1) gold chloride that 5mL concentration is 0.5mM preparation gold kind: is added into the CTAB solution that 5mL concentration is 0.1M
(HAuCl4) aqueous solution, it is then uniformly mixed, then the ultrapure water of 14mL is added thereto；To above-mentioned solution under conditions of vortex
In to rapidly join 0.5mL concentration be the ice-cold sodium borohydride (NaBH of 0.1M4) solution, solution becomes royal purple, continues violent
Stirring 2 minutes, then places 3h in 28 DEG C of waters, will not participate in the NaBH of reaction4Gold kind of solution is made in all hydrolysis, standby
With；
(2) gold nanorods solution is prepared: by the gold chloride (HAuCl of 5mL 1mM4) with the cetyl bromination of 5mL 0.2M
Ammonium (CTAB) mixes well, and sequentially adds the silver nitrate (AgNO that 200uL concentration is 4mM3) solution, 70uL 100mM Vitamin C
Sour (AA), is vigorously stirred, and solution is become colorless by yellow, finally, gold kind of the solution 120uL prepared in step (1) is added, gently
It is placed in after shaking up in 28 DEG C of water-baths and reacts 12h, it is gold nanorods solution that solution, which becomes darkviolet,；Then the gold that will be prepared
Nanometer rods solution is centrifuged 10min at 12000rpm, is dispersed in pure water again after removing supernatant liquor.Again repeated centrifugation and
The operating procedure for removing supernatant removes extra CTAB, and finally the gold nanorods solution after washing is kept in dark place at 4 DEG C.
Embodiment 3:
Prepare the gold nanorods (BSA-GNRs) of bovine serum albumin package: the gold nanorods for taking 500uL embodiment 2 to prepare are molten
Liquid is placed on metal bath and in 1.5mL centrifuge tube controlled at 37 DEG C, injects the BSA solution 250ul of 20mg/mL,
It mixes；Add water that the total volume of entire solution is made so that BSA is sufficiently reacted with gold nanorods to 1mL, static 30min；By solution
It is centrifuged 10 minutes at 2000rpm, twice；Precipitating is dispersed back into the pure water of 1mL and is kept in dark place at 4 DEG C；
Embodiment 4:
It prepares gold nanoclusters gold nanorods composite nanoparticle (GNC-GNRs): taking the gold nanorods of 500uL embodiment 2 molten
Liquid is placed on metal bath and in 1.5mL centrifuge tube controlled at 37 DEG C, injects the gold nanoclusters of 300uL embodiment 1
Solution mixes；Add water to make the total volume of entire solution to 1mL, static 30min, keeps gold nanoclusters and gold nanorods abundant
Solution, is then centrifuged 10 minutes by reaction at 10000rpm, and precipitating is dispersed back into the pure water of 1mL again after being repeated once
It is kept in dark place at 4 DEG C；
By GNRs, BSA-GNRs, GNC-GNRs (OD=0.8) of same concentrations and ultrapure water, with near-infrared, (808nm connects
Continuous wave (CW) is 2.97W) illumination 5 minutes, measure its ramp case；It repeats illumination 3 times.
The results showed that
Fig. 1 shows gold nanorods (GNRs), the gold nanorods after BSA is modified of ascorbic acid reduction preparation
(BSA-GNRs) ultraviolet spectra of the gold nanorods (GNC-GNRs) and after gold nanoclusters are modified.UV- shown in Fig. 1
In vis-NIR spectrum, compound later since gold nanorods surface recombination thin layer, refractive index change with BSA and GNC progress
Become, slight red shift has occurred in surface plasmon resonance peak.In the spectrum of GNC gold nanorods compound particle, longitudinal plasma
Formant does not broaden significantly, and shape is not substantially change, this two kinds of nanoparticle of explanation has carried out effectively in pure water
Assembling, and favorable dispersibility after assembling.
Fig. 2 shows gold nanorods (GNRs) (A), the gold nanorods after BSA is modified of ascorbic acid reduction preparation
(BSA-GNRs) transmission electron microscope (TEM) image of (B) and the gold nanorods (GNC-GNRs) (C) after gold nanoclusters are modified.
No matter GNRs or BSA-GNRs, GNC-GNRs have good monodispersity to the TEM image explanation of Fig. 2.And pass through TEM
Image we can it is visible in detail by BSA package gold nanorods (B) have the shell that a slice width degree is about 3nm in outer rim
Layer, this again demonstrate the surfaces that BSA is effectively wrapped in gold nanorods.In the TEM image (C) of GNC-GNRs, Ke Yiguan
It is the grey shell of 3nm that observing, which not only has a layer thickness at the edge of gold nanorods, and about 1nm black is also distributed in shell
Gold nano grain, the proof gold nanorods that this equally can be strong are wrapped up wherein by the gold nanoclusters of template of BSA.
The electrostatic interaction between these nanoparticles has been probed into the measurement of Zeta potential.Gold nanorods are due to its surface
CTAB duplicature show electropositive (ζ=+ 31.5mV), and the BSA that gold nanoclusters wrap ups due to its surface is so show elecrtonegativity.Institute
With two kinds of particles since electrostatic interaction interacts together.
Fig. 3 shows pure water, gold nanoclusters (GNC), ascorbic acid and restores the gold nanorods (GNRs) of preparation, by BSA
Gold nanorods (BSA-GNRs) after modification and gold nanorods (GNC-GNRs) sample solution after gold nanoclusters are modified exist
By the average ramp case after 3 reirradiations (808nm, 2.97W).In the average heating column after 3 repetition illumination
In shape figure, we can clearly be observed: pure water and gold nanoclusters the solution temperature after illumination only increase 2.03 DEG C, and
Unmodified gold nanorods temperature increases 13.13 DEG C, since the package BSA-GNRs solution temperature of BSA increases 18.37
DEG C, it is 5.24 DEG C higher than naked gold nanorods solution temperature.It is amazing to be, when gold nanoclusters in gold nanorods surface modification
Afterwards, solution increases 27.63 DEG C at identical conditions, increases 14.5 DEG C than common golden stick, increases than BSA-GNRs
9.16℃.Strong the demonstrating of these data can be improved effectively by the method in gold nanorods surface modification gold nanoclusters
The light thermal property of golden stick.
Fig. 4 shows gold nanorods (GNRs) (A), the gold nanorods after BSA is modified of ascorbic acid reduction preparation
(BSA-GNRs) sample solution (B) and gold nanorods (GNC-GNRs) sample solution (C) after gold nanoclusters are modified are at 3 times
The heating curve of reirradiation (808nm, 2.97W).Heating curve is also the important evidence for verifying gold nano-material light thermal property
One of.We can be clearly seen that in heating curve figure, by the heating speed of the gold nanorods (BSA-GNRs) of BSA package
The slightly above common golden stick of rate, and nanoparticle (GNC-GNRs) heating rate after gold nanoclusters are compound has and greatly mentions
Height has averagely reached 4.71 DEG C/min；And the golden stick heating rate of common golden stick and BSA package is only 2.23 DEG C/min and 3.27
℃/min。
By observing heating curve, we are also found that common gold nanorods (GNRs) (A) heat up after irradiation
Apparent decaying is happened.In the 1st irradiation (808nm, 2.97W, 5min), solution temperature is increased to 42.9 DEG C afterwards, and the 2nd
Temperature is 40.6 DEG C after secondary irradiation, and only up to 39.7 DEG C after the 3rd irradiation.Gold nanorods are after the package by BSA
(B) although biocompatibility enhances, colloidal stability is declined.BSA-GNRs solution has occurred in irradiation process
Coagulation, temperature damping's is more obvious, and temperature has been increased to 49.3 DEG C after irradiating for the first time, and temperature is 46.3 DEG C after the 2nd irradiation,
3 DEG C are had dropped than the 1st time；Temperature has only reached 43.5 DEG C after 3rd irradiation, irradiates compared to the 1st time, temperature totally reduces
5.8℃.And the composite nano materials (GNC-GNRs) after gold nanoclusters are modified showed on photo and thermal stability it is very excellent,
The heating curve of reirradiation has almost no change three times, and final temperature is kept at 53 DEG C or so.
Fig. 5 shows the gold nanorods (GNRs) of ascorbic acid reduction preparation, after BSA is modified and by gold nanoclusters
Nanorods Samples solution after modification is in transmission electron microscope (TEM) photo after 3 reirradiations (808nm, 2.97W).It is logical
TEM image after crossing the irradiation in Fig. 5 it can be seen that, (808nm, 2.97W, 5min are repeated after the irradiation of the same terms
3 times), it is unmodified gold stick, BSA package golden stick different degrees of deformation occurs, from it is rodlike change be fused into disk or
Person's little particle.And the golden stick (GNC-GNRs) after gold nanoclusters wrap up then still keeps complete rodlike.This data with
Heating curve mutually echoes.
It was therefore concluded that due to the limitation of gold nanoclusters, the light thermal property of these gold nanorods (GNC-GNRs)
It is greatly improved, deformation is significantly inhibited, while being radiated thermal stability and also being greatly improved.
Embodiment 5:
Prepare gold nanoclusters (GNC) solution of bovine serum albumin(BSA) (BSA) package:
The HAuCl for being 10mM by 5mL concentration4It is sufficiently mixed with 5mL concentration for the BSA of 50mg/mL, is filled at 37 DEG C
Dividing and stir, after 2min, rapidly joins the brand-new NaOH that 0.5mL concentration is 1M, continuation is stirred at 37 DEG C, after reacting 12h,
Solution be it is orange red, be placed in camera bellows be irradiated with the light of 365nm watch red fluorescence i.e. GNC synthesis finish；
Embodiment 6:
Gold nanorods (GNRs) solution of dopamine reduction is prepared with crystal seed growth method:
(1) preparation gold kind: the HAuCl for being 10mM by 250uL concentration4It is abundant for the CTAB solution of 0.1M with 9.75mL concentration
It mixes, is rapidly injected 600uL 0.01M brand-new NaBH4, is vigorously stirred, solution becomes dark-brown from yellow immediately, continues to stir
After 2min, it is spare to be placed in 28 DEG C of water-bath 4h；
(2) gold nanorods solution is prepared: by the HAuCl of 500uL 10mM4With
9.50mL concentration is that the CTAB solution of 0.1M mixes well, and mixed liquor is placed on 40 DEG C of metal baths and stands 10min.
The AgNO that 70uL concentration is 0.1M is sequentially added later3Solution, 500uL concentration are 40mg/mL brand-new dopamine (DA) solution, are shaken
Even, solution becomes light yellow from yellow, finally, golden kind of the solution of injection 160uL above method preparation, anti-in 42.5 DEG C of metal baths
3h is answered, it is gold nanorods solution that solution, which becomes sepia,；Then by the gold nanorods solution prepared at 12000rpm from
Heart 10min is dispersed in pure water again after removing supernatant liquor, and repeatedly aforesaid operations remove extra CTAB again, will wash
It is kept in dark place at 4 DEG C of gold nanorods solution afterwards, it is spare.
Embodiment 7:
Prepare bovine serum albumin package gold nanorods (BSA-GNRs): take the gold nanorods solution of 500uL embodiment 6 in
It in 1.5mL centrifuge tube, is placed on metal bath, injects the BSA solution 250uL of 20mg/mL, mix；Adding water to make will be entire molten
The total volume of liquid enables BSA sufficiently to react with gold nanorods to 1mL, static 30min；Solution is centrifuged 10 at 2000rpm
Minute, twice；Precipitating is dispersed back into the pure water of 1mL and is kept in dark place at 4 DEG C.
Embodiment 8:
It prepares gold nanoclusters gold nanorods composite nanoparticle (GNC-GNRs): taking the gold nanorods of 500uL embodiment 6 molten
Liquid is placed on metal bath and in 1.5mL centrifuge tube controlled at 37 DEG C, injects the gold nanoclusters of 300ul embodiment 5
Solution mixes；Water is added to make to obtain gold nanoclusters and gold nanorods sufficiently the total volume of entire solution to 1mL, static 30min
Solution, is then centrifuged 10 minutes by reaction at 11000rpm, and precipitating is dispersed back into the pure water of 1mL again after being repeated once
It is kept in dark place at 4 DEG C.
By GNRs, BSA-GNRs, GNC-GNRs (OD=0.8) of same concentrations and ultrapure water, with near-infrared, (808nm connects
Continuous wave (CW) is 2.97W) illumination 5 minutes, measure its ramp case.It repeats illumination 3 times.
The results showed that
Fig. 6 shows gold nanorods (GNRs), the gold nanorods (BSA- after BSA is modified of dopamine reduction preparation
GNRs the ultraviolet spectra of the gold nanorods (GNC-GNRs)) and after gold nanoclusters are modified.In the UV-vis-NIR spectrum of Fig. 6
In, longitudinal plasma resonance peak (LSPR) 914nm for the gold nanorods not being wrapped be in BSA and GNC carry out it is compound after
Since gold nanorods surface recombination thin layer, refractive index change, apparent red shift is had occurred in surface plasmon resonance peak.?
In the spectrum of GNC gold nanorods compound particle, longitudinal plasma resonance peak does not broaden significantly, and shape is not substantially change,
This two kinds of nanoparticle of explanation is effectively assembled in pure water, and favorable dispersibility after assembling.
Fig. 7 shows gold nanorods (GNRs) (A), the gold nanorods after BSA is modified of dopamine reduction preparation
(BSA-GNRs) transmission electron microscope (TEM) image of (B) and the gold nanorods (GNC-GNRs) (C) after gold nanoclusters are modified.
No matter gold nanorods or BSA-GNRs, GNC-GNRs have good monodispersity to TEM image explanation in Fig. 7.And
By TEM image we can the gold nanorods visible in detail by BSA package to have a slice width degree in outer rim be about 3nm's
Shell, this again demonstrate the surfaces that BSA is effectively wrapped in gold nanorods.In the TEM image of GNC-GNRs, it can observe
Not only having a layer thickness to the edge in gold nanorods is the grey shell of 3nm, and the gold of about 1nm black is also distributed in shell
Nano particle, the proof gold nanorods that this equally can be strong are wrapped up wherein by the gold nanoclusters of template of BSA.
The electrostatic interaction between these nanoparticles has been probed into the measurement of Zeta potential.Gold nanorods are due to its surface
CTAB duplicature show electropositive (ζ=+ 23.4mV), and the BSA that gold nanoclusters wrap ups due to its surface is so show elecrtonegativity.Institute
With two kinds of particles since electrostatic interaction interacts together.
Fig. 8 shows pure water, gold nanoclusters (GNC), dopamine and restores the gold nanorods (GNRs) of preparation, repairs by BSA
Gold nanorods (BSA-GNRs) and gold nanorods (GNC-GNRs) sample solution after gold nanoclusters are modified are passing through 3 after decorations
Average ramp case after secondary reirradiation (808nm, 2.97W).The average heating after 3 repetition illumination in fig. 8
In histogram, we can clearly be observed, pure water and gold nanoclusters the solution temperature after illumination only increase 1.03 DEG C,
And unmodified gold nanorods temperature increases 7.67 DEG C of since the package BSA-GNRs solution temperature of BSA increases 8.63
DEG C, it is about 1 DEG C higher than naked golden stick solution temperature.It is amazing to be, after gold nanoclusters in golden stick surface modification, identical
Under the conditions of solution increase 15.97 DEG C, increase 8.3 DEG C than common golden stick, increase 9.16 DEG C than BSA-GNRs.These data
Strong demonstrates the light thermal property that golden stick can be effectively improved by the method in gold nanorods surface modification gold nanoclusters.
Fig. 9 shows gold nanorods (GNRs), the gold nanorods (BSA- after BSA is modified of dopamine reduction preparation
GNRs gold nanorods (GNC-GNRs) sample solution) and after gold nanoclusters are modified by 3 reirradiations (808nm,
Transmission electron microscope photo after 2.97W).By irradiation after TEM image it can be seen that, after the irradiation of the same terms
(808nm, 2.97W, 5min are repeated 3 times), the gold nanorods that unmodified gold nanorods, BSA are wrapped up occur in various degree
Deformation, from it is rodlike change be fused into disk or deformation.And the gold nanorods after gold nanoclusters wrap up then still are kept
It is complete rodlike.This knot data is mutually echoed with heating curve.
It was therefore concluded that the light thermal property of these gold nanorods has greatly due to the limitation of gold nanoclusters
It improves, deformation is significantly inhibited, while being radiated thermal stability and also being greatly improved.
Method in the present invention mainly utilizes the electrostatic interaction between gold nanoclusters and gold nanorods, to make two kinds of nanometers
Material interaction forms new composite nano materials together.
Specifically, since the good biocompatibility of gold nanoclusters makes the gold modified through gold nanoclusters
Nanometer rods toxicity is significantly reduced, and has good organism application prospect.
The deficiencies of photo and thermal stability that the present invention reports before solving is poor, toxic.Using the present invention, facilitate further
Biomolecule modification and biomedical aspect application.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (9)
1. a kind of method for enhancing its light thermal property and stability by modifying gold nanoclusters to gold nanorods surface, special
Sign is, includes at least following steps:
(1), gold nanorods (GNRs) solution is prepared；
(2), gold nanoclusters (GNC) solution of bovine serum albumin (BSA) package is prepared；
(3), gold nanoclusters gold nanorods composite material (GNC-GNRs) is prepared by electrostatic interaction；
Wherein, in step (1), by gold nanorods milli-Q water, it is centrifuged off supernatant, and disperse again；
When reducing agent is ascorbic acid, gold nanorods solution is prepared with the following method: gold chloride (HAuCl4) with 5mL 0.2M's
Cetyl ammonium bromide (CTAB) mixes well, and sequentially adds the silver nitrate (AgNO that 200uL concentration is 4mM3) solution, 70uL
The ascorbic acid (AA) of 100mM, is vigorously stirred, and solution is become colorless by yellow, finally, golden kind of the solution of 120uL is added, gently shakes
It is placed in after even in 28 DEG C of water-baths and reacts 12h, it is gold nanorods solution that solution, which becomes darkviolet,；
When reducing agent is dopamine (DA), gold nanorods solution is prepared with the following method: by gold chloride (HAuCl4) with
9.50mL concentration is that cetyl ammonium bromide (CTAB) solution of 0.1M mixes well, and mixed liquor is placed in quiet on 40 DEG C of metal baths
Set 10min；The AgNO that 70uL concentration is 0.1M is sequentially added later3Solution, 500uL concentration are 40mg/mL brand-new dopamine
(DA) solution shakes up, and solution becomes light yellow from yellow, finally, golden kind of the solution of injection 160uL, reacts in 42.5 DEG C of metal baths
3h, it is gold nanorods solution that solution, which becomes sepia,；
In step (2), by gold chloride (HAuCl4) be sufficiently mixed with bovine serum albumin (BSA), after stirring, NaOH solution is added,
Continue to stir, reaction 12-15 hour after, solution be it is orange red, be placed in be irradiated in camera bellows with the light of 365nm and watch red
Fluorescence, that is, gold nanoclusters (GNC) synthesis finishes；
In step (3), gold nanorods solution is placed in centrifuge tube, controlled at 36-38 DEG C on metal bath, injection step
Suddenly the gold nanoclusters solution of (2) mixes；Add water to make volume 1mL, the static 20-45min of entire solution, make gold nanoclusters with
Gold nanorods, which obtain, sufficiently to react；
Wherein, the particle edge of preparation-obtained modified gold nanorods has bovine serum albumin (BSA) shell, in cow's serum egg
Gold nanoclusters particle is distributed in white (BSA) shell.
2. the method according to claim 1, wherein in step (1),
Gold nanorods are synthesized with golden kind of a growth method, use cetyl trimethylammonium bromide (CTAB) as stabilizer；
The concentration of the gold nanorods aqueous solution is 0.2nM；
The gold nanorods of synthesis can remove extra cetyl ammonium bromide (CTAB) by centrifugation；
Each centrifugation time is 9-11min, and centrifugation number is twice；
After being centrifuged twice, dispersed again using neutral ultrapure water.
3. the method according to claim 1, wherein in step (2),
Gold chloride (HAuCl4) solution concentration be 10mM, volume 5mL；
Bovine serum albumin (BSA) solution concentration is 50mg/mL；
Reacting optimum temperature is 37 DEG C.
4. the method according to claim 1, wherein in step (3),
The concentration of gold nanorods solution is 0.2nM, volume 500uL；
The volume of gold nanoclusters is 150uL-450uL；
Reacting optimum temperature is 37 DEG C.
5. the method according to claim 1, wherein further include step (4),
In step (4), purified by the way of being centrifuged twice；
Centrifugation revolution used is 8000-10000rpm；
Centrifugation time is 9-12 minutes；
Composite nanoparticle after purification, which is divided equally, to be scattered in ultrapure water.
6. a kind of modified gold nanorods, which is characterized in that any method is prepared in -5 according to claim 1.
7. modified gold nanorods according to claim 6, which is characterized in that
Bovine serum albumin (BSA) shell thickness is greater than 2nm；
The gold nanoclusters particle greater than 0.5nm is distributed in bovine serum albumin (BSA) shell.
8. modified gold nanorods according to claim 6, which is characterized in that
By OD value be 0.8 composite modified solution of gold nanoparticles with 808nm near-infrared continuous wave illumination 5 minutes of 2.97W, tool
There are the data of following light thermal property:
Heating rate is more than 3.5 DEG C/min.
9. modified gold nanorods according to claim 8, which is characterized in that
Composite nanoparticle solution is after irradiation 5 minutes, in the data at least one following photo and thermal stability: heating
Rate is no more than 12% decaying；It is substantially undeformed in electron microscopic picture；Ultraviolet spectra is substantially unchanged.
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| CN109773176B (en) * | 2019-01-23 | 2020-12-01 | 苏州大学 | Method for modulating optical section of gold nanorod on single wavelength |
| CN110280779B (en) * | 2019-07-12 | 2021-10-26 | 太原理工大学 | Core-shell type nanogold composite material, and preparation method and application thereof |
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