CN106141201A - A kind of method improving gold nanorods light thermal property and photo and thermal stability - Google Patents
A kind of method improving gold nanorods light thermal property and photo and thermal stability Download PDFInfo
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- CN106141201A CN106141201A CN201610740984.6A CN201610740984A CN106141201A CN 106141201 A CN106141201 A CN 106141201A CN 201610740984 A CN201610740984 A CN 201610740984A CN 106141201 A CN106141201 A CN 106141201A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides the gold nanorods of a kind of modification, it is coated with the gold nanoclusters wrapped up by bovine serum albumin (BSA), constitutes a kind of novel nano complex.This complex is exposed under the irradiation of near infrared light for probing into its light thermal property and stability.After the near infrared light repeatedly circulated, there is not significant change in optical property and the pattern of gold nanoclusters gold nanorods complex, heats up significantly raised.As a comparison, successively by identical gold nanorods and bovine serum albumin trapping gold nanometer rods as stability control experiment.It addition, the light thermal property of gold nanoclusters gold nanorods complex and colloidal stability have fabulous repeatability.Therefore, this raising light thermal property, the nano-complex of photo and thermal stability are 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 method improving gold nanorods photo and thermal stability.Be specifically related to by with bovine serum albumin bag
The electrostatic interaction of the gold nanoclusters wrapped up in is compound thus improves warm performance, photo and thermal stability and the biocompatibility of gold nanorods
Method.
Background technology
Near infrared light refers to wavelength electromagnetic wave near infrared region (780nm 2526nm).Relative to ultraviolet light and
For visible ray, near-infrared laser irradiates can penetrate into deep layer subcutaneous tissue, and the injury pole of the health tissues to surrounding
Little.And many nano-particle, such as copper sulphide nano crystalline substance, gold nanorods, Golden Triangle sheet etc., all have in near-infrared wavelength district
Unique surface plasmon absorption.Based on the optical property that this is special, with near infrared light, these nano materials are entered
Row can produce certain heat after irradiating.And by changing the intensity of laser, irradiation duration, the concentration of fluid sample
Deng, thus it is possible to vary produce heat number, carry out quantitatively regulating and controlling.Therefore, there is the nano material of near-infrared absorption as light
The fields such as thermit powder is just being extensively studied and is being applied to drug release, cancer diagnosis and treatment, sensor.
Gold nanoclusters (GNC, Gold Nanocluster), is a kind of by the combination of ten several atoms to tens atom
One-tenth, diameter are less than the nanoparticle of 2 nanometers.Since GNC is found, due to its less size and excellent fluorescence property and
Good biocompatibility has a wide range of applications at aspects such as tumor cell imagings.The bovine serum albumin of its surface parcel
(BSA) it is a kind of common protein, cheap, simple and easy to get；But this does not hinder it wide in terms of biologic applications
Development prospect.Especially in the organism application aspect of the nanoparticle quickly grown in recent years, BSA is used to increase nanoparticle
The biocompatibility of son, help nanoparticle carry out endocytosis exocytosis etc..
Gold nanorods (GNR) is as a photo-thermal therapy agent near infrared region region response, to cancerous cell and tumor
Destructive power very notable, there is in terms of photo-thermal therapy vast potential for future development.It is well known, however, that gold nano
Rod has bigger bio-toxicity due to cetyl trimethylammonium bromide (CTAB) duplicature on its surface.And GNR is at warp
Can deform upon when crossing laser emission, photo-thermal effect reduces.These unfavorable factors limit it and further apply.
These nano materials can be improved owing to gold nanorods (GNR) and bovine serum albumin (BSA) are compound to control at radiant heat
Performance and composite in treatment have remarkable biocompatibility, so this research receives substantial amounts of concern in the recent period.
But currently available technology document does not also carry out green high-efficient about the gold nanoclusters wrapped up by bovine serum albumin is compound
Gold nanorods surface modified and improve its photo and thermal stability and the report of biocompatibility successful case.
Summary of the invention
One object of the present invention, is to provide a kind of method improving gold nanorods light thermal property and photo and thermal stability,
It can solve the problem that gold nanorods is as a near-infrared response light hot material stability, problem that light thermal property is not good enough.
One object of the present invention, is to provide a kind of method improving gold nanorods light thermal property and photo and thermal stability,
It can improve the biocompatibility of the gold nanorods after modification.
One object of the present invention, is to provide a kind of method improving gold nanorods light thermal property and photo and thermal stability,
The method is convenient and reliable.
One object of the present invention, is to provide a kind of method improving gold nanorods light thermal property and photo and thermal stability,
Have in above-mentioned purpose is two or more.
One object of the present invention, is to provide the gold nanorods of a kind of modification, and it can solve the problem that gold nanorods is as one
Individual near-infrared response light hot material stability, the problem that light thermal property is not good enough, and/or can solve the problem that the gold nano after modification
The biocompatibility of rod.
An aspect of of the present present invention, it is provided that a kind of method improving gold nanorods light thermal property and photo and thermal stability, Qi Zhongjin
Nanometer rods is gold nanoclusters parcel ascorbic acid or the gold nanorods composite nano materials of dopamine reduction, and it at least includes as follows
Step:
(1) gold nanorods (GNRs) solution, is prepared；
(2) gold nanoclusters (GNC) solution that bovine serum albumin (BSA) wraps up, is prepared；
(3), gold nanoclusters gold nanorods composite (GNC-GNRs) is prepared by electrostatic interaction.
In step (1), by gold nanorods milli-Q water, it is centrifuged off supernatant, and again disperses；
Preferably, gold nanorods gold kind growth method synthesizes, with cetyl trimethylammonium bromide (CTAB) conduct
Stabilizer；
Preferably, when reducing agent is ascorbic acid, gold nanorods solution is adopted with the following method when preparing: gold chloride
(HAuCl4) fully mix with the cetyl ammonium bromide (CTAB) of 5mL 0.2M, it is sequentially added into the nitric acid that 200uL concentration is 4mM
Silver (AgNO3) solution, the ascorbic acid (AA) of 70uL 100mM, be stirred vigorously, solution is become colorless by yellow, finally, add
120uL gold kind solution, is positioned in 28 DEG C of water-baths reaction 12h after shaking up gently, solution becomes darkviolet, and to be gold nanorods molten
Liquid；
Preferably, when reducing agent is dopamine (DA), gold nanorods solution is adopted with the following method when preparing: by HAuCl4With
9.50mL concentration is that the CTAB solution of 0.1M fully mixes, and mixed liquor is placed on 40 DEG C of metal baths standing 10min；The most successively
Adding 70uL concentration is the AgNO of 0.1M3Solution, 500uL concentration are 40mg/mL brand-new dopamine (DA) solution, shake up, solution
Being become light yellow from yellow, finally, inject 160uL gold kind solution, react 3h at 42.5 DEG C of metal baths, solution becomes sepia i.e.
For gold nanorods solution；
Preferably, the concentration of described gold nanorods aqueous solution is 0.2nM；
Preferably, the gold nanorods of synthesis can be removed by centrifugation unnecessary CTAB；
Preferably, each centrifugation time is 9-11min, and centrifugal number of times is twice；It is furthermore preferred that centrifugation time is 9 every time
Minute, 10 minutes or 11 minutes；
Preferably, after two times centrifugal, the ultra-pure water of neutrality is used again to disperse；
Preferably, in step (2), by gold chloride (HAuCl4) be sufficiently mixed with BSA, after stirring, add NaOH solution,
Continuing stirring, after reacting 12-15 hour, solution is orange red, is placed in camera bellows and is irradiated watching redness with the light of 365nm
Fluorescence i.e. GNC synthesis is complete；
Preferably, the chlorauric acid solution concentration used is 10mM, and volume is 5mL；Bovine serum albumen solution concentration is 50mg/
ML, volume is 50mL；
Preferably, reaction optimum temperature is 37 DEG C；
Preferably, the response time is 12 hours；
Preferably, the response time is 13 hours；
Preferably, the response time is 14 hours；
Preferably, the response time is 15 hours.
Preferably, in step (3), being placed in centrifuge tube by gold nanorods solution, controlling temperature on metal bath is 36-
38 DEG C, the gold nanoclusters solution of implantation step (2), mixing；Adding water and making the volume of whole solution is 1mL, and static 20-45min makes
Gold nanoclusters is fully reacted with gold nanorods；
Preferably, the concentration of gold nanorods solution is 0.2nM, and volume is 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.
Further, step (4) is also included: purification gold nanoclusters golden nanometer particle composite nanoparticle.
Preferably, in step (4), the mode of two times centrifugal is used to be purified；
Preferably, centrifugal revolution used is 8000-10000rpm；It is further preferred that centrifugal used revolution be 8000rpm,
9000rpm、10000rpm rpm；It is furthermore preferred that centrifugal revolution used is 9000rpm；
Preferably, centrifugation time is 9-12 minute, more preferably 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 ultra-pure water；
Preferably, centrifugal rotational speed is 10000rpm, and the time is 10 minutes.
Another aspect of the present invention, it is provided that a kind of modified gold nanorods, it is to use above method to prepare, and has good
Good light thermal property and stability.
Modified gold nanorods provided by the present invention, wherein, the particle of this modification gold nanorods, the limit of gold nanorods particle
Edge has BSA shell, and gold nanoclusters granule is distributed in BSA shell.Preferably, BSA shell thickness is more than 2nm；Preferably,
BSA shell thickness is about 3nm；Preferably, in BSA shell, more than 0.5nm gold nanoclusters granule is distributed；Preferably, exist
The gold nanoclusters granule of about 1nm is distributed in BSA shell.
Modified gold nanorods provided by the present invention, wherein, uses the composite modified gold nanorods solution that OD value is 0.8
The 808nm near-infrared continuous wave illumination of 2.97W 5 minutes, has data of following light thermal property: heating rate 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, after irradiating 5 minutes, has the data of following photo and thermal stability: heat up
The speed decay less than 12%；In electron microscopic picture undeformed；Ultraviolet spectra is unchanged.
Method in the present invention mainly utilizes the electrostatic between bovine serum albumin and the gold nanorods on gold nanoclusters surface to make
With, so that two kinds of nano materials interact and define new composite nano materials together.
By the formation mechenism of gold nanoclusters gold nanorods composite nanoparticle it can be concluded that through surface modified
Nanoparticle destroyed due to CTAB duplicature, so having outstanding biocompatibility, therefore the method is the biggest
Solve the restriction that nano material is applied at biological field.
Especially interesting, owing to the water solublity of gold nanoclusters makes the gold nanorods modified through gold nanoclusters show as
Water solublity, has good colloidal stability.
The present invention solves that the light thermal property reported before is not good enough, poor stability, the deficiency such as poisonous.Utilize the present invention, have
Help the modification of further biomolecule and the application at biomedical aspect, such as remote sensing, bio-imaging and photo-thermal therapy.
Accompanying drawing explanation
Fig. 1. the gold nanorods (GNRs) of ascorbic acid reduction preparation, the gold nanorods (BSA-after BSA modifies
The ultraviolet spectra of the gold nanorods (GNC-GNRs) GNRs) and after gold nanoclusters is modified.
Fig. 2. the gold nanorods (GNRs) (A) of ascorbic acid reduction preparation, the gold nanorods (BSA-after BSA modifies
GNRs) (B) and the transmission electron microscope of the gold nanorods (GNC-GNRs) (C) after gold nanoclusters is modified.
Fig. 3. pure water (Pure water), gold nanoclusters (GNCs), ascorbic acid reduction preparation gold nanorods (GNRs),
Gold nanorods (BSA-GNRs) after BSA modifies and gold nanorods (GNC-GNRs) sample after gold nanoclusters is modified
Solution is at the average ramp case after 3 reirradiations (808nm, 2.97W).
Fig. 4. the gold nanorods (GNRs) (A) of ascorbic acid reduction preparation, the gold nanorods (BSA-after BSA modifies
GNRs) (B) and gold nanorods (GNC-GNRs) (C) sample solution after gold nanoclusters is modified are at 3 reirradiations
The heating curve of (808nm, 2.97W).
Fig. 5. the gold nanorods (GNRs) of ascorbic acid reduction preparation, the gold nanorods (BSA-after BSA modifies
GNRs) gold nanorods (GNC-GNRs) sample solution and after gold nanoclusters is modified through 3 reirradiations (808nm,
Transmission electron microscope photo after 2.97W).
Fig. 6. the gold nanorods (GNRs) of dopamine reduction preparation, the gold nanorods (BSA-GNRs) after BSA modifies
Ultraviolet spectra with the gold nanorods (GNC-GNRs) after gold nanoclusters is modified.
Fig. 7. the gold nanorods (GNRs) (A) of dopamine reduction preparation, the gold nanorods (BSA-after BSA modifies
GNRs) (B) and the transmission electron microscope of the gold nanorods (GNC-GNRs) (C) after gold nanoclusters is modified.
Fig. 8. the gold nanorods (GNRs) of pure water (Pure water), gold nanoclusters (GNCs), dopamine reduction preparation, warp
Cross the gold nanorods (BSA-GNRs) after BSA modifies and gold nanorods (GNC-GNRs) sample after gold nanoclusters is modified is molten
Liquid is at the average ramp case after 3 reirradiations (808nm, 2.97W).
Fig. 9. dopamine reduction preparation gold nanorods (GNRs), through BSA modify after gold nanorods (BSA-GNRs) and
Gold nanorods (GNC-GNRs) after gold nanoclusters is modified is in the transmission after 3 reirradiations (808nm, 2.97W)
Electromicroscopic photograph.
Detailed description of the invention
Below in conjunction with specific embodiment further describe the present invention, advantages of the present invention and feature will be with describe and
Apparent.But embodiment is only exemplary, the scope of the present invention is not constituted any restriction.Those skilled in the art should
It should be appreciated that, the details of technical solution of the present invention and form can be repaiied lower without departing from the spirit and scope of the present invention
Change or replace, but these amendments and replacement each fall within protection scope of the present invention.
Preparation method in following embodiment, if no special instructions, is conventional method；Experiment material used, such as nothing
Specified otherwise, is routine biochemistry chemical reagent work and is purchased and can buy.
Embodiment 1:
Gold nanoclusters (GNC) solution that preparation is wrapped up with bovine serum albumin (BSA):
It is the HAuCl of 10mM by 5mL concentration4It is sufficiently mixed with the BSA that 5mL concentration is 50mg/mL, fills at 37 DEG C
Dividing stirring, after 2min, rapidly joining 0.5mL concentration is 1M brand-new NaOH, continues to be stirred at 37 DEG C, after reaction 12h, molten
Liquid is orange red, is placed in camera bellows and is irradiated watching red fluorescence i.e. GNC synthesis complete with the light of 365nm.
Embodiment 2:
Gold nanorods (GNRs) solution that ascorbic acid (AA) reduces is prepared by seeded growth method:
(1) preparation gold is planted: adding 5mL concentration in the CTAB solution that 5mL concentration is 0.1M is the gold chloride of 0.5mM
(HAuCl4) aqueous solution, then mix homogeneously, then it is added thereto to the ultra-pure water of 14mL；To above-mentioned solution under conditions of vortex
In to rapidly join 0.5mL concentration be sodium borohydride (NaBH ice-cold for 0.1M4) solution, solution becomes royal purple, continues acutely
Stir 2 minutes, in 28 DEG C of waters, place 3h subsequently, the NaBH of reaction will not participated in4All hydrolysis, prepare gold and plant solution, standby
With；
(2) gold nanorods solution is prepared: by the gold chloride (HAuCl of 5mL 1mM4) and the cetyl bromination of 5mL 0.2M
Ammonium (CTAB) fully mixes, and is sequentially added into the silver nitrate (AgNO that 200uL concentration is 4mM3) solution, the Vitamin C of 70uL 100mM
Acid (AA), is stirred vigorously, and solution is become colorless by yellow, finally, adds the gold of preparation in step (1) and plants solution 120uL, gently
Being positioned in 28 DEG C of water-baths reaction 12h after shaking up, solution becomes darkviolet and is gold nanorods solution；Then the gold that will prepare
Nanometer rods solution is centrifugal 10min under 12000rpm, is again dispersed in pure water after removing the supernatant.Again repeated centrifugation and
The operating procedure removing supernatant removes unnecessary CTAB, is finally kept in Dark Place at 4 DEG C by the gold nanorods solution after washing.
Embodiment 3:
Prepare the gold nanorods (BSA-GNRs) of bovine serum albumin parcel: the gold nanorods taking 500uL embodiment 2 preparation is molten
Liquid is in 1.5mL centrifuge tube, and being positioned on metal bath and controlling temperature is 37 DEG C, injects the BSA solution 250ul of 20mg/mL,
Mixing；Add water make the cumulative volume of whole solution to 1mL, static 30min, make BSA fully be reacted with gold nanorods；By solution
Under 2000rpm centrifugal 10 minutes, twice；It is dispersed back into precipitation in the pure water of 1mL keeping in Dark Place at 4 DEG C；
Embodiment 4:
Prepare gold nanoclusters gold nanorods composite nanoparticle (GNC-GNRs): the gold nanorods taking 500uL embodiment 2 is molten
Liquid is in 1.5mL centrifuge tube, and being positioned on metal bath and controlling temperature is 37 DEG C, injects the gold nanoclusters of 300uL embodiment 1
Solution, mixing；Add water make the cumulative volume of whole solution to 1mL, static 30min, make gold nanoclusters and gold nanorods be able to fully
Reaction, is then centrifuged solution 10 minutes under 10000rpm, precipitation is dispersed back in the pure water of 1mL after being repeated once again
Keep in Dark Place at 4 DEG C；
By GNRs, BSA-GNRs, GNC-GNRs (OD=0.8) and ultra-pure water near-infrared (808nm, the company of same concentrations
Continuous ripple (CW) is 2.97W) illumination 5 minutes, measure its ramp case；Repeat illumination 3 times.
Test result indicate that:
Fig. 1 shows the gold nanorods (GNRs) of ascorbic acid reduction preparation, the gold nanorods after BSA modifies
(BSA-GNRs) ultraviolet spectra of the gold nanorods (GNC-GNRs) and after gold nanoclusters is modified.At the UV-shown in Fig. 1
In vis-NIR spectrum, with BSA and GNC carry out compound after due to gold nanorods surface recombination thin layer, refractive index changes
Becoming, surface plasmon resonance peak there occurs slight red shift.In the spectrum of GNC gold nanorods compound particle, longitudinal plasma
Formant the most significantly broadens, and shape the most substantially changes, and these two kinds of nanoparticles of explanation have been carried out effectively in pure water
Assemble, and favorable dispersibility after assembling.
Fig. 2 shows the gold nanorods (GNRs) (A) of ascorbic acid reduction preparation, the gold nanorods after BSA modifies
(BSA-GNRs) (B) and transmission electron microscope (TEM) image of the gold nanorods (GNC-GNRs) (C) after gold nanoclusters is modified.
The TEM image of Fig. 2 illustrates that GNRs or BSA-GNRs, GNC-GNRs have good monodispersity.And pass through TEM
Image we can gold nanorods (B) shell that has a slice width degree to be about 3nm in outer rim through BSA parcel visible in detail
Layer, this again demonstrates BSA and is effectively wrapped in the surface of gold nanorods.In the TEM image (C) of GNC-GNRs, Ke Yiguan
Observe and do not only have the Lycoperdon polymorphum Vitt shell that a layer thickness is 3nm at the edge of gold nanorods, in shell, about 1nm black is also distributed
Gold nano grain, this strongest proof gold nanorods is wrapped in wherein by the gold nanoclusters with BSA as template.
The mensuration of Zeta potential has probed into the electrostatic interaction between these nanoparticles.Gold nanorods is due to its surface
CTAB duplicature show electropositive (ζ=+ 31.5mV), and the BSA that gold nanoclusters wraps up due to its surface is so aobvious elecrtonegativity.Institute
Interact together due to electrostatic interaction with two kinds of particles.
Fig. 3 shows the gold nanorods (GNRs) of pure water, gold nanoclusters (GNC), ascorbic acid reduction preparation, through BSA
Gold nanorods (BSA-GNRs) after modification and gold nanorods (GNC-GNRs) sample solution after gold nanoclusters is modified exist
Average ramp case after 3 reirradiations (808nm, 2.97W).At the post that averagely heats up after 3 times are repeated illumination
In shape figure, we can clearly observe: pure water and gold nanoclusters solution temperature after illumination only increases 2.03 DEG C, and
The most modified gold nanorods temperature increases 13.13 DEG C, owing to the parcel BSA-GNRs solution temperature of BSA increases 18.37
DEG C, higher than naked gold nanorods solution temperature 5.24 DEG C.Amazing, when upper gold nanoclusters is modified on gold nanorods surface
After, solution increases 27.63 DEG C at identical conditions, adds 14.5 DEG C than common gold rod, increases than BSA-GNRs
9.16℃.What these data were strong demonstrates by can effectively improve in the method for gold nanorods surface modification gold nanoclusters
The light thermal property of gold rod.
Fig. 4 shows the gold nanorods (GNRs) (A) of ascorbic acid reduction preparation, the gold nanorods after BSA modifies
(BSA-GNRs) sample solution (B) and gold nanorods (GNC-GNRs) sample solution (C) after gold nanoclusters is modified are at 3 times
The heating curve of reirradiation (808nm, 2.97W).Heating curve is also the important evidence of checking gold nano-material light thermal property
One of.In heating curve figure we it can be clearly seen that, through BSA parcel gold nanorods (BSA-GNRs) intensification speed
The slightly above common gold rod of rate, and nanoparticle (GNC-GNRs) heating rate after gold nanoclusters is compound has had and carries greatly
Height, has averagely reached 4.71 DEG C/min；And commonly the golden rod heating rate of gold rod and BSA parcel is only 2.23 DEG C/min and 3.27
℃/min。
By observing heating curve, we are it is also found that common gold nanorods (GNRs) (A) is heating up after irradiating
Situation there occurs significantly decay.Irradiate (808nm, 2.97W, 5min) solution temperature afterwards at the 1st time and be increased to 42.9 DEG C, the 2nd
After secondary irradiation, temperature is 40.6 DEG C, and only up to 39.7 DEG C after irradiating for the 3rd time.Gold nanorods is after the parcel of BSA
(B) although biocompatibility enhances, but colloidal stability has declined.BSA-GNRs solution there occurs in irradiation process
Coagulation, temperature damping becomes apparent from, and after irradiating first, temperature has been increased to 49.3 DEG C, and after irradiating for the 2nd time, temperature is 46.3 DEG C,
Have dropped 3 DEG C than the 1st time；After irradiating for 3rd time, temperature has only reached 43.5 DEG C, irradiates compared to the 1st time, and temperature totally reduces
5.8℃.And the composite nano materials (GNC-GNRs) after gold nanoclusters is modified shows the most excellent on photo and thermal stability,
The heating curve of three reirradiations has almost no change, and final temperature is kept at about 53 DEG C.
Fig. 5 shows the gold nanorods (GNRs) of ascorbic acid reduction preparation, after BSA modifies and through gold nanoclusters
Nanorods Samples solution after modification is at transmission electron microscope (TEM) photo after 3 reirradiations (808nm, 2.97W).Logical
Cross the TEM image after the irradiation in Fig. 5 it can be seen that, after the irradiation of the same terms (808nm, 2.97W, 5min, repeat
3 times), all there is deformation in various degree in the most modified gold rod, the gold rod of BSA parcel, from bar-shaped change be fused into disk or
The little granule of person.Gold rod (GNC-GNRs) after gold nanoclusters wraps up the most still keeps complete bar-shaped.These data with
Heating curve mutually echoes.
It was therefore concluded that, due to the restriction of gold nanoclusters, the light thermal property of these gold nanorods (GNC-GNRs)
Being greatly improved, deformation is significantly inhibited, and radiant heat stability also drastically increases simultaneously.
Embodiment 5:
Prepare gold nanoclusters (GNC) solution that bovine serum albumin (BSA) wraps up:
It is the HAuCl of 10mM by 5mL concentration4It is sufficiently mixed with the BSA that 5mL concentration is 50mg/mL, fills at 37 DEG C
Divide stirring, after 2min, rapidly join brand-new NaOH that 0.5mL concentration is 1M, continue to be stirred at 37 DEG C, after reaction 12h,
Solution is orange red, is placed in camera bellows and is irradiated watching red fluorescence i.e. GNC synthesis complete with the light of 365nm；
Embodiment 6:
With seeded growth method prepare dopamine reduction gold nanorods (GNRs) solution:
(1) preparation gold is planted: be the HAuCl of 10mM by 250uL concentration4Abundant with the CTAB solution that 9.75mL concentration is 0.1M
Mixing, is rapidly injected 600uL 0.01M brand-new NaBH4, is stirred vigorously, and solution is become dark-brown from yellow immediately, continues stirring
After 2min, it is placed in 28 DEG C of water-bath 4h standby；
(2) gold nanorods solution is prepared: by the HAuCl of 500uL 10mM4With
9.50mL concentration is that the CTAB solution of 0.1M fully mixes, and mixed liquor is placed on 40 DEG C of metal baths standing 10min.Afterwards
It is sequentially added into the AgNO that 70uL concentration is 0.1M3Solution, 500uL concentration are 40mg/mL brand-new dopamine (DA) solution, shake up,
Solution is become light yellow from yellow, finally, injects gold kind solution prepared by 160uL said method, reacts at 42.5 DEG C of metal baths
3h, solution becomes sepia and is gold nanorods solution；Then the gold nanorods solution prepared is centrifuged under 12000rpm
10min, is dispersed in pure water after removing the supernatant again, again repeats aforesaid operations and removes unnecessary CTAB, after washing
Gold nanorods solution 4 DEG C at keep in Dark Place, standby.
Embodiment 7:
Prepare the gold nanorods (BSA-GNRs) of bovine serum albumin parcel: take the gold nanorods solution of 500uL embodiment 6 in
In 1.5mL centrifuge tube, it is positioned on metal bath, injects the BSA solution 250uL of 20mg/mL, mixing；Add water and make whole molten
The cumulative volume of liquid to 1mL, static 30min, make BSA fully be reacted with gold nanorods；Solution is centrifuged under 2000rpm 10
Minute, twice；It is dispersed back into precipitation in the pure water of 1mL keeping in Dark Place at 4 DEG C.
Embodiment 8:
Prepare gold nanoclusters gold nanorods composite nanoparticle (GNC-GNRs): the gold nanorods taking 500uL embodiment 6 is molten
Liquid is in 1.5mL centrifuge tube, and being positioned on metal bath and controlling temperature is 37 DEG C, injects the gold nanoclusters of 300ul embodiment 5
Solution, mixing；Add water and make the cumulative volume of whole solution to 1mL, static 30min, make gold nanoclusters and gold nanorods obtain fully
Reaction, is then centrifuged solution 10 minutes under 11000rpm, precipitation is dispersed back in the pure water of 1mL after being repeated once again
Keep in Dark Place at 4 DEG C.
By GNRs, BSA-GNRs, GNC-GNRs (OD=0.8) and ultra-pure water near-infrared (808nm, the company of same concentrations
Continuous ripple (CW) is 2.97W) illumination 5 minutes, measure its ramp case.Repeat illumination 3 times.
Test result indicate that:
Fig. 6 show dopamine reduction preparation gold nanorods (GNRs), through BSA modify after gold nanorods (BSA-
The ultraviolet spectra of the gold nanorods (GNC-GNRs) GNRs) and after gold nanoclusters is modified.UV-vis-NIR spectrum at Fig. 6
In, longitudinal plasma resonance peak (LSPR) 914nm of the most wrapped gold nanorods is in after carrying out being combined with BSA and GNC
The thin layer due to gold nanorods surface recombination, refractive index changes, surface plasmon resonance peak there occurs obvious red shift.?
In the spectrum of GNC gold nanorods compound particle, longitudinal plasma resonance peak the most significantly broadens, and shape the most substantially changes,
These two kinds of nanoparticles of explanation have carried out effectively assembling in pure water, and favorable dispersibility after assembling.
Fig. 7 shows the gold nanorods (GNRs) (A) of dopamine reduction preparation, the gold nanorods after BSA modifies
(BSA-GNRs) (B) and transmission electron microscope (TEM) image of the gold nanorods (GNC-GNRs) (C) after gold nanoclusters is modified.
TEM image in Fig. 7 illustrates that gold nanorods or BSA-GNRs, GNC-GNRs have good monodispersity.And
By TEM image, we can have a slice width degree to be about 3nm's in outer rim by the gold nanorods through BSA parcel visible in detail
Shell, this again demonstrates BSA and is effectively wrapped in the surface of gold nanorods.In the TEM image of GNC-GNRs, can observe
Do not only have the Lycoperdon polymorphum Vitt shell that a layer thickness is 3nm to the edge at gold nanorods, in shell, the gold of about 1nm black is also distributed
Nano-particle, this strongest proof gold nanorods is wrapped in wherein by the gold nanoclusters with BSA as template.
The mensuration of Zeta potential has probed into the electrostatic interaction between these nanoparticles.Gold nanorods is due to its surface
CTAB duplicature show electropositive (ζ=+ 23.4mV), and the BSA that gold nanoclusters wraps up due to its surface is so aobvious elecrtonegativity.Institute
Interact together due to electrostatic interaction with two kinds of particles.
Fig. 8 shows the gold nanorods (GNRs) of pure water, gold nanoclusters (GNC), dopamine reduction preparation, repaiies through BSA
After decorations, gold nanorods (BSA-GNRs) and gold nanorods (GNC-GNRs) sample solution after gold nanoclusters is modified are through 3
Average ramp case after secondary reirradiation (808nm, 2.97W).The average intensification after 3 times are repeated illumination in fig. 8
In block diagram, we can clearly observe, pure water and gold nanoclusters solution temperature after illumination only increases 1.03 DEG C,
And the most modified gold nanorods temperature increases 7.67 DEG C. owing to the parcel BSA-GNRs solution temperature of BSA increases 8.63
DEG C, higher about 1 DEG C than naked gold rod solution temperature.Amazing, after upper gold nanoclusters is modified on gold rod surface, identical
Under the conditions of solution increase 15.97 DEG C, add 8.3 DEG C than common gold rod, increase 9.16 DEG C than BSA-GNRs.These data
Strong demonstrates the light thermal property that can effectively be improved gold rod by the method modifying gold nanoclusters on gold nanorods surface.
Fig. 9 shows the gold nanorods (GNRs) of dopamine reduction preparation, the gold nanorods (BSA-after BSA modifies
GNRs) gold nanorods (GNC-GNRs) sample solution and after gold nanoclusters is modified through 3 reirradiations (808nm,
Transmission electron microscope photo after 2.97W).By irradiate after TEM image it can be seen that, after the irradiation of the same terms
(808nm, 2.97W, 5min are repeated 3 times), the most modified gold nanorods, the gold nanorods of BSA parcel all occur in various degree
Deformation, be fused into disk or deformation from bar-shaped change.Gold nanorods after gold nanoclusters wraps up then still keeps
Complete is bar-shaped.This footing is according to mutually echoing with heating curve.
It was therefore concluded that, due to the restriction of gold nanoclusters, the light thermal property of these gold nanorods has had greatly
Improving, deformation is significantly inhibited, and radiant heat stability also drastically increases simultaneously.
Method in the present invention mainly utilizes the electrostatic interaction between gold nanoclusters and gold nanorods, so that two kinds of nanometers
Material interacts and defines new composite nano materials together.
Especially interesting, owing to the good biocompatibility of gold nanoclusters makes the gold through gold nanoclusters modification
Nanometer rods toxicity is significantly reduced, and has good organism application prospect.
The present invention solves the deficiencies such as the photo and thermal stability reported before is poor, poisonous.Utilize the present invention, contribute to further
Biomolecule modify and in the application of biomedical aspect.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1., by gold nanoclusters is modified the method that gold nanorods surface strengthens its light thermal property and stability, it is special
Levy and be, at least comprise the steps:
(1) gold nanorods (GNRs) solution, is prepared；
(2) gold nanoclusters (GNC) solution that bovine serum albumin (BSA) wraps up, is prepared；
(3), gold nanoclusters gold nanorods composite (GNC-GNRs) is prepared by electrostatic interaction.
Method the most according to claim 1, it is characterised in that in step (1), by gold nanorods milli-Q water,
It is centrifuged off supernatant, and again disperses；
Preferably, gold nanorods gold is planted growth method and is synthesized, with cetyl trimethylammonium bromide (CTAB) as stable
Agent；
Preferably, when reducing agent is ascorbic acid, gold nanorods solution is adopted with the following method when preparing: gold chloride (HAuCl4) with
The cetyl ammonium bromide (CTAB) of 5mL 0.2M fully mixes, and is sequentially added into the silver nitrate (AgNO that 200uL concentration is 4mM3)
Solution, the ascorbic acid (AA) of 70uL100mM, be stirred vigorously, and solution is become colorless by yellow, finally, adds 120uL gold kind molten
Liquid, is positioned in 28 DEG C of water-baths reaction 12h after shaking up gently, solution becomes darkviolet and is gold nanorods solution；
Preferably, when reducing agent is dopamine (DA), gold nanorods solution is adopted with the following method when preparing: by HAuCl4With 9.50mL
Concentration is that the CTAB solution of 0.1M fully mixes, and mixed liquor is placed on 40 DEG C of metal baths standing 10min；It is sequentially added into afterwards
70uL concentration is the AgNO of 0.1M3Solution, 500uL concentration are 40mg/mL brand-new dopamine (DA) solution, shake up, and solution is by Huang
Complexion changed is light yellow, finally, injects 160uL gold kind solution, reacts 3h at 42.5 DEG C of metal baths, and solution becomes sepia and is gold
Nanometer rods solution；
Preferably, the concentration of described gold nanorods aqueous solution is 0.2nM；
Preferably, the gold nanorods of synthesis can remove unnecessary CTAB by centrifugal；
Preferably, each centrifugation time is 9-11min, and centrifugal number of times is twice；It is furthermore preferred that every time centrifugation time be 9 minutes,
10 minutes or 11 minutes；
Preferably, after two times centrifugal, the ultra-pure water of neutrality is used again to disperse.
Method the most according to claim 1, it is characterised in that in step (2), by gold chloride (HAuCl4) abundant with BSA
Mixing, after stirring, adds NaOH solution, continues stirring, and after reacting 12-15 hour, solution is orange red, is placed in camera bellows use
The light of 365nm is irradiated watching red fluorescence i.e. GNC synthesis complete；
Preferably, chlorauric acid solution concentration is 10mM, and volume is 5mL；
Bovine serum albumen solution concentration is 50mg/mL, and volume is 50mL；
Preferably, reaction optimum temperature is 37 DEG C；
Preferably, the response time is 12 hours；
Preferably, the response time is 13 hours；
Preferably, the response time is 14 hours；
Preferably, the response time is 15 hours.
Method the most according to claim 1, it is characterised in that in step (3), gold nanorods solution is placed in centrifuge tube
In, metal bath controls temperature and is 36-38 DEG C, the gold nanoclusters solution of implantation step (2), mixing；Add water and make whole solution
Volume be 1mL, static 20-45min, make gold nanoclusters obtain with gold nanorods and fully react；
Preferably, the concentration of gold nanorods solution is 0.2nM, and volume is 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 it is static
Time is 30 minutes.
Method the most according to claim 1, it is characterised in that also include step (4), purification gold nanoclusters golden nanometer particle
Composite nanoparticle；
Preferably, in step (4), the mode of two times centrifugal is used to be purified；
Preferably, centrifugal revolution used is 8000-10000rpm；It is further preferred that centrifugal used revolution be 8000rpm,
9000rpm、10000rpm rpm；It is furthermore preferred that centrifugal revolution used is 9000rpm；
Preferably, centrifugation time is 9-12 minute, more preferably 9 minutes, 10 minutes, 11 minutes, 12 minutes, during it is further preferred that be centrifuged
Between be 10 minutes；
Preferably, composite nanoparticle after purification is divided equally and is scattered in ultra-pure water；
Preferably, centrifugal rotational speed is 10000rpm, and the time is 10 minutes.
6. a modified gold nanorods, it is characterised in that prepare according to described method arbitrary in claim 1-5.
7. a modified gold nanorods, it is characterised in that
The particle of this modification gold nanorods, the edge of gold nanorods particle has BSA shell, Jenner is distributed in BSA shell
Rice bunch granule.
Modified gold nanorods the most according to claim 7, it is characterised in that
Preferably, BSA shell thickness is more than 2nm；
Preferably, BSA shell thickness is about 3nm；
Preferably, in BSA shell, more than 0.5nm gold nanoclusters granule is distributed；
Preferably, in BSA shell, the gold nanoclusters granule of about 1nm is distributed.
9. a modified gold nanorods, it is characterised in that
By the 808nm near-infrared continuous wave illumination 5 minutes of composite modified solution of gold nanoparticles 2.97W that OD value is 0.8, tool
There are data of 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
℃/min。
Modified gold nanorods the most according to claim 9, it is characterised in that
Composite nanoparticle solution, after irradiating 5 minutes, has in the data of at least one following photo and thermal stability: heat up
The speed decay less than 12%；Preferably, the most undeformed in electron microscopic picture；Preferably, ultraviolet spectra is the most unchanged.
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