CN105036070B - Gold nanorod-silicon dioxide core-shell structure nanometer material, preparation method and application - Google Patents
Gold nanorod-silicon dioxide core-shell structure nanometer material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a gold nanorod-silicon dioxide core-shell structure nanometer material. The core structure of the core-shell structure nanometer material is a chiral gold nanorod side-by-side assembly with the circular dichroism optical activity. The shell structure of the core-shell structure nanometer material is silicon dioxide. The core of the chiral gold nanorod side-by-side assembly is coated with the silicon dioxide shell layer, so that the nanometer material with the circular dichroism optical activity is obtained. According to the nanometer material, the side-by-side assembly structure is stable, the solution state is stable, and the circular dichroism optical activity is obviously improved, wherein the circular dichroism optical activity is improved by 4-6 times compared with a pure chiral gold nanorod, and the stability is kept as long as 6 months. A preparation method of the gold nanorod-silicon dioxide core-shell structure nanometer material is simple and low in cost. The obtained chiral gold nanorod side-by-side assembly-silicon dioxide core-shell structure nanometer material has various compositions and properties, is wide in application range and has the large development space.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of gold nanorods-silicon dixoide nucleocapsid structure nano material, preparation
Method and purposes, particularly to a kind of chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material and its preparation side
Method, described chirality core-shell structured nanomaterials have circular dichroism optical activity and good stability.
Background technology
Noble metal nano particles because of its unique surface plasma resonance, in bio-imaging, photonic device, chemistry
The field such as sensing and biological therapy has a wide range of applications.
It was discovered by researchers that when chiral molecules is connected on gold nanorods surface, chiral molecules can induce noble metal
Nano-particle produces optical activity (govorov, the a.o. being located at visual field；fan,z.y.；hernandez,p.；slocik,
j.m.；naik,r.r.theory of circular dichroism ofnanomaterials comprising chiral
molecules and nanocrystals:plasmon enhancement,dipole interactions,and
dielectric effectsnano lett.2010,10,1374.).However, being lived using the optics that spherical nano-particle obtains
Property is very faint, does not have advantage in application aspect.Gold nanorods, compared to spherical nano-particle, due to its anisotropic knot
The point effect that structure leads to, can make its surface electromagnetic field further enhance.Therefore, using gold nanorods assembly, study people
Member (zhu, z.n.；liu,w.j.；li,z.t.；han,b.；zhou,y.l.；gao,y.；tang,z.y.manipulat ion
of collective optical activity in one-dimensional plasmonic assemblyacs
Nano2012,6,2326.) regulation and control can be carried out in visible region to this optical activity and amplify further.
The enhanced optical activity of chiral gold nano-rod assembly, has obtained application in the detection of dna.As
Cn103487378a discloses a kind of method that circular dichroism based on gold nanorod aggregation detects dna.However, it is chiral in this
Gold nanorods assembly is to produce in the solution, and its package assembly stability is poor, easily settles, and leads to optical activity in time not
Can keep, greatly affect its application in actually detected.
The stability how improving chiral gold nano-rod assembly is this area one problem demanding prompt solution.
Content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of gold nanorods-silica core-shell
Structure nano material, the nuclear structure of described core-shell structured nanomaterials is to have circular dichroism optically active chirality gold nanorods shoulder
Assembly shoulder to shoulder, shell structure is silica.
The thickness of shell structure silica of the present invention is 20～50nm, preferably 30～40nm；
Described chirality gold nanorods are shoulder to shoulder in assembly, number >=2 of gold nanorods, and preferably 3～10；
Preferably, the draw ratio of described gold nanorods is 2～5:1, preferably 3～4:1.
In gold nanorods-silicon dixoide nucleocapsid structure nano material that the present invention provides, specific gold nanorods major diameter
Than and assembling number can produce stronger circular dichroism optical activity, and coat the silica of specific thicknesses, can stably tie up
Hold the self-assembled structures shoulder to shoulder of gold nanorods, and do not interfere with the circular dichroism optical activity of gold nanorods assembly.
The second object of the present invention is to provide a kind of gold nanorods-silicon dixoide nucleocapsid structure as described in one of purpose to receive
The preparation method of rice material, methods described comprises the steps:
(1) prepare chiral gold nanorods assembly shoulder to shoulder；
(2) by chiral gold nanorods assembly coated silica shell in alcohol-water system shoulder to shoulder, obtain chiral gold
Nano-rod assembly@silicon dixoide nucleocapsid structure nano material.
Present invention coated silica under alcohol-water system, can adjust hydrolysis rate and the gold nanorods of tetraethyl orthosilicate
Assembling speed matches, and obtains and has the optically active gold nanorods of strong circular dichroism-silicon dixoide nucleocapsid structure nano material；
On the other hand, alcohol-water system can greatly shorten the time of coated silica shell.
The preparation process of step (1) of the present invention described chirality gold nanorods assembly shoulder to shoulder is:
Gold nanorods are dispersed in the aqueous solution containing cationic surfactant, add the chirality with sulfydryl little afterwards
Molecule and sodium citrate form chiral gold nanorods assembly shoulder to shoulder.
In step (1) aqueous solution, the concentration of gold nanorods is 0.8～1.2nmol/l, such as 0.95nmol/l,
0.98nmol/l, 1.03nmol/l, 1.09nmol/l, 1.12nmol/l, 1.17nmol/l etc., preferably 1nmol/l.
Preferably, in the gold nanorods aqueous solution of 1nmol/l, the concentration of cationic surfactant is 0.4～
1mmol/l, the concentration of the chiral small molecule with sulfydryl is 1～10 μm of ol/l, and the concentration of sodium citrate is 20～50 μm of ol/l.
Preferably, in the gold nanorods aqueous solution of 1nmol/l, surfactant, the chiral small molecule with sulfydryl and lemon
The concentration of lemon acid sodium is 0.5mmol/l, 10 μm of ol/l and 50 μm of ol/l.
In the present invention, the effect of described cationic surfactant is the assembling speed controlling gold nanorods, addition
Too low, gold nanorods assembling process can be led to too fast, be far longer than the hydrolysis rate of the tetraethyl orthosilicate that step (2) adds, lead
Gold nanorods are caused to shift to an earlier date coagulation it is impossible to obtain stable product；Addition is too high, and gold nanorods assembling speed is too low, and shell coats
Gold nanorods cannot be formed and assemble shoulder to shoulder.
In the present invention, sodium citrate addition very little, can lead to not formed gold nanorods shoulder to shoulder assembly it is impossible to
Obtain that there is the optically active product of enhanced circular dichroism.
Preferably, the draw ratio of described gold nanorods is 2～5:1, preferably 3～4:1.
The assembling shoulder to shoulder of the gold nanorods of specific draw ratio is more beneficial for formation, and to have strong circular dichroism optically active
Gold nanorods self-assembly.
Preferably, described cationic surfactant is cetyl trimethylammonium bromide.
Preferably, the described chiral small molecule containing sulfydryl is cysteine, reduced form paddy light ammonia peptide and n- mucolyticum
The mixing of any a kind or at least 2 kinds in acid, preferably cysteine.
Cysteine of the present invention can be l type cysteine or d type cysteine.
The step of step (2) of the present invention described chirality gold nanorods assembly coated silica shell shoulder to shoulder is:
The chiral gold nanorods obtaining to step (1) add alcohol in the assembly aqueous solution shoulder to shoulder, adjust solution ph to 8～
10, add tetraethyl orthosilicate, after stirring is reacted, obtain chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer
Material.
The described alcohol of step (2) is the mixture of any a kind or at least 2 kinds in methyl alcohol, ethanol or isopropanol.
Preferably, the volume ratio of the addition of described alcohol and the aqueous solution is 1:3～1:5, such as 1:3.3,1:3.8,1:
4.5th, 1:4.9 etc., preferably 1:4.
Preferably, after described tetraethyl orthosilicate adds, in reaction solution, the concentration of tetraethyl orthosilicate is 5～9mmol/l, example
As 6mmol/l, 7mmol/l, 8mmol/l etc..
Tetraethyl orthosilicate concentration is too low, such as less than 5mmol/l, gold nanorods assembly can be led to cannot to coat complete two
Silica shell, the stability of impact nano material, causes gold nanorods all to precipitate.
Preferably, the temperature of described reaction is 20～30 DEG C, preferably 21 DEG C, 23 DEG C, 27 DEG C, 29 DEG C etc., the time is 2～
5h, such as 2.5h, 3h, 3.5h, 4h, 4.5h etc., preferably 3h.
As optimal technical scheme, the preparation of gold nanorods of the present invention-silicon dixoide nucleocapsid structure nano material
Method comprises the steps:
(1) draw ratio is that 2～5:1 gold nanorods are dispersed in the aqueous solution containing cationic surfactant, afterwards
The chiral small molecule with sulfydryl and sodium citrate is added to form chiral gold nanorods assembly shoulder to shoulder；Wherein, the described aqueous solution
In, the concentration of gold nanorods is 1nmol/l, and the concentration of surfactant is 500 μm of ol/l, the chiral small molecule with sulfydryl dense
Spend for 10 μm of ol/l, the concentration of sodium citrate is 50 μm of ol/l；
(2) add alcohol in the chiral gold nanorods that step (1) obtains shoulder to shoulder the assembly aqueous solution, make alcohol/water volume
Ratio controls in 1:4, adjusts solution ph to 9, adds tetraethyl orthosilicate, obtains chiral gold nano-rod assembly@bis- after stirring reaction
Silica core-shell structured nanomaterials.
The third object of the present invention is to provide a kind of gold nanorods-silicon dixoide nucleocapsid structure as described in one of purpose to receive
The purposes of rice material, described gold nanorods-silicon dixoide nucleocapsid structure nano material is used as the enhancing substrate of chiral molecules, preferably
Trace detection for chiral biomolecule and NO free radical.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention passes through, in the gold nanorods assembly core coating silica shell shoulder to shoulder with chirality, to obtain
Obtained nano material optically active with circular dichroism, the package assembly shoulder to shoulder of described nano material is stable, and solution state is steady
Calmly, circular dichroism optical activity has and significantly improves, and the circular dichroism optical activity of more simple chiral gold nanorods improves 4～6
Times, stability is up to 6 months；
(2) preparation method of gold nanorods-silicon dixoide nucleocapsid structure nano material that the present invention provides is simple, cost
Low, the composition of chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material preparing, property are various, application
Scope is wide, has larger development space.
Brief description
The extinction spectra figure of the gold nanorods that Fig. 1 obtains for embodiment 5 step (1)；
The transmission electron micrograph of the gold nanorods that Fig. 2 obtains for embodiment 5 step (1)；
Gold nanorods assembly and the extinction spectra of unassembled gold nanorods that Fig. 3 obtains for embodiment 3～5 step (2)
Figure；
Fig. 4 is the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure that embodiment 1～2 and comparative example 1～2 obtain
The transmission electron microscope picture (a is comparative example 1, and b is comparative example 2, and c is embodiment 1, and d is embodiment 2) of nano material；
Fig. 5 receives for the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure of embodiment 3,4,5 and comparative example 3 preparation
The transmission electron microscope photo (a is comparative example 3, and b is embodiment 3, and c is embodiment 4, and d is embodiment 5) of rice material；
The circle of the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material that Fig. 6 obtains for embodiment 3～5
Dichroscope is composed
The chiral gold nanorods that Fig. 7 obtains for the embodiment 4 circular dichroism optical activity of assembly and its in time shoulder to shoulder
Change；
Fig. 8 is the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer that embodiment 5,6 and comparative example 6 obtain
The circular dichroism of material；
The circle two of the chiral gold nanosphere assembly silicon dixoide nucleocapsid structure nano material that Fig. 9 obtains for comparative example 11
Color spectrum；
The chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material that Figure 10 obtains for embodiment 5 is in time
Change circular dichroism.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Experimental technique in following embodiments, if no special instructions, is conventional method；Experiment material used, such as no
Specified otherwise, is commercially available available from routine biochemistry chemical reagent work.
In following examples；Tem transmission electron microscope photo is obtained using tecnai g2f20s-twin transmission electron microscope；Ultraviolet can
See that absorption spectrum adopts ultraviolet-visual spectrometer (hitachi u-3010) to obtain；Circular dichroism adopts circular dichroism instrument
(jasco j-1500 spectropolarimeter) obtains.
Embodiment
A kind of chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material, is prepared via a method which to obtain:
(1) seed mediated growth method prepares gold nanorods:
1. the synthesis of crystal seed: by the nabh of the 10mmol/l of 0.15ml4Solution is quickly adding into 10ml and contains 0.25mmol/
L sodium citrate and 0.125mmol/l haucl4Mixed liquor in, after stirring 2min, be placed in 23 DEG C of waters bath with thermostatic control standing, after 2h
Standby；
2. the generation of gold nanorods: contain 0.1mol/lctab, 0.5mmol/lhaucl to 10ml4, 0.055mmol/l resist
The crystal seed that 12 μ l step (1) synthesize is added, after standing 12h, after purification in the mixed liquor of bad hematic acid and 0.06mmol/l silver nitrate
It is concentrated into 1nmol/l, add cetyl trimethylammonium bromide and obtain gold nanorods solution for standby；Ten in described gold nanorods solution
The concentration of six alkyl trimethyl ammonium bromides is designated as cctab；
With transmission electron microscope and ultravioletvisible absorption spectrophotometer, above-mentioned solution is characterized:
(2) prepare chiral gold nanorods assembly shoulder to shoulder, comprise the steps:
3. take the gold nanorods solution 5.6ml of step (1) seed law synthesis, addition certain volume concentration is 100 μm of ol/l
Cysteine and certain volume concentration be 1mmol/l sodium citrate, stir, chiral gold nanorods can be obtained shoulder to shoulder
Assembly；Described gold nanorods GOLD FROM PLATING SOLUTION nanometer rods concentration is 1nmol/l；The concentration of cysteine is designated as cCysteine；Described gold
In nanometer rods solution, the concentration of citric acid is designated as cSodium citrate；
Characterize the formation of chiral gold nano-rod assembly using ultraviolet-visible absorption spectroscopy and circular dichroism；
(3) synthesis of chiral gold nanorods assembly@silicon dixoide nucleocapsid structure nano material, comprises the steps:
4. add ethanol in 5.6ml chiral gold nano-rod assembly solution, volume is vEthanol, adjust ph to 9.0 (ph value
Can float between 8～10), add the tetraethyl orthosilicate of 15wt%, volume is vTetraethyl orthosilicate, after stirring reaction, obtain chiral Jenner
Rice rod assembly@silicon dixoide nucleocapsid structure nano material；The time of described stirring reaction is t；Whipping temp controls 20～
30℃；
Characterized using transmission electron microscope and obtain chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material；To core
Shell structure carries out circular dichroism sign.
The reaction condition of table 1 embodiment 1～12
Note: 1.. in embodiment 1～13, the concentration of each reactant is with respect to the numerical value of 1nmol/l gold nanorods.
Comparative example 1～10
Preparation process is identical with embodiment, and difference is following reaction condition, and table 2 is the reaction condition of comparative example 1～10.
The reaction condition of table 2 comparative example 1～10
Note: 1.. in comparative example 1～10, the concentration of each reactant is with respect to the numerical value of 1nmol/l gold nanorods.
Comparative example 11
Preparation process is same as Example 5, and difference is to replace gold nanorods as core by the use of gold nanosphere, is assembled
With cladding experiment.
Comparative example 12
Preparation process is same as Example 5, differs only in and is added without ethanol in step solution 4., after reaction 5h, and
Do not generate chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material；Until reacting to 20h, there is no chirality yet
Gold nanorods assembly@silicon dixoide nucleocapsid structure nano material.
By comparative example 12 as can be seen that during coated silica, the addition of ethanol can greatly accelerate titanium dioxide
The cladding speed of silicon.
The gold nanorods that embodiment 1～13 step (1) is obtained carry out the photometric sign of ultravioletvisible absorption light, Fig. 1
The extinction spectra figure of the gold nanorods obtaining for embodiment 5 step (1), shows that the gold nanorods of synthesis in this method have well
Dispersiveness；Embodiment 1～4 is similar with Fig. 1 with the extinction spectra figure of 6～13 gold nanorods obtaining；
The gold nanorods that embodiment 1～13 step (1) is obtained carry out transmission electron microscope scanning, and Fig. 2 is embodiment 5
The transmission electron microscope of the gold nanorods that step (1) obtains scans it is seen that gold nanorods are about 43.8nm, and diameter is about
13.8nm；The gold nanorods that embodiment 1～4 and 6～13 obtains are through transmission electron microscope scanning it was demonstrated that the length of gold nanorods
Footpath ratio all in the range of 2～5:1, such as 2.2:1,2.4:1,2.7:1,3:1,3.5:1,4:1,4.2:1,4.7:1 etc..
The gold nanorods assembly that embodiment 1～13 step (2) is obtained carries out the photometric table of ultravioletvisible absorption light
Levy, gold nanorods assembly and the extinction spectra figure of unassembled gold nanorods that Fig. 3 obtains for embodiment 3～5 step (2), phase
Ratio in unassembled gold nanorods, chiral gold nanorods self-assembly major axis absworption peak blue shift, this phenomenon confirm gold nanorods true
Define assembly shoulder to shoulder in fact；When sodium citrate concentration becomes big, the major axis absworption peak of chiral gold nanorods self-assembly is blue
Move bigger, illustrate that the number of gold nanorods in the gold nanorod chiral self-assembly being formed increases；
Fig. 4 is the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure that embodiment 1～2 and comparative example 1～2 obtain
The transmission electron microscope picture (a is comparative example 1, and b is comparative example 2, and c is embodiment 1, and d is embodiment 2) of nano material；Can by Fig. 4 a
To find out, when in gold nanorods solution, the concentration of cetyl trimethylammonium bromide is 0.3mmol/l (comparative example 1), gold nano
Excellent assembling process is too fast, is far longer than the hydrolysis rate of tetraethyl orthosilicate, leads to gold nanorods to shift to an earlier date coagulation it is impossible to be stablized
Coated with silica gold nanorods assembly product；Cetyl front three in gold nanorods solution be can be seen that by Fig. 4 b
When the concentration of base ammonium bromide is 1.5mmol/l (comparative example 1), surfactant concentration is too high, and sodium citrate cannot induce its group
Dress, gold nanorods cannot complete to assemble, and the nanostructured obtaining is the silicon dixoide nucleocapsid structure of single gold nanorods, does not have
There is circular dichroism optical activity.And the cetyl front three being 0.4～1mmol/l containing concentration is can be seen that by Fig. 4 c and Fig. 4 d
The gold nanorods solution of base ammonium bromide can obtain the gold nanorods assembly product of stable coated with silica, has strong
Circular dichroism optical activity.
Fig. 5 receives for the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure of embodiment 3,4,5 and comparative example 3 preparation
The transmission electron microscope photo (a is comparative example 3, and b is embodiment 3, and c is embodiment 4, and d is embodiment 5) of rice material；Permissible by Fig. 4 a
Find out, sodium citrate addition is≤20 μm of ol/l, gold nanorods cannot form assembly, products therefrom is coated with silica
Single gold nanorods, can be seen that from Fig. 5 b～5d and be gradually increased with sodium citrate concentration (20 μm of ol/l, 30 μm of ol/l, 50
μm ol/l), the assembling degree of gold nanorods assembly shoulder to shoulder is gradually increased, and can obtain coating different number gold nanorods
Chiral core shell structure.And the experiment condition of comparative example 4, because gold nanorods assembling speed is too fast, more than the water of tetraethyl orthosilicate
Solution speed, no stable product generate.
The circle of the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material that Fig. 6 obtains for embodiment 3～5
Dichroscope is composed it can be seen that the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material preparing has relatively
Strong circular dichroism optical activity, and its circular dichroism optical activity is gradually increased (20 μm of ol/l, 30 μ with sodium citrate concentration
Mol/l, 50 μm of ol/l) can be regulated and controled in visual field.
The chiral gold nanorods that Fig. 7 obtains for the embodiment 4 circular dichroism optical activity of assembly and its in time shoulder to shoulder
Change, shoulder to shoulder in the assembling process of assembly, the concentration of sodium citrate is 50 μm of ol/l to described chirality gold nanorods；Jenner
Assembly is occurring in that stronger circular dichroism signal it was demonstrated that this is a kind of hand corresponding to its major axis absorption peak position to rice rod shoulder to shoulder
The gold nanorods assembly of property, but, assembly stability is poor shoulder to shoulder for chiral gold nanorods, and its circular dichroism optical activity is one
Disappear after it.
Fig. 8 is the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer that embodiment 5,6 and comparative example 6 obtain
The circular dichroism of material it can be seen that be 10 μm of ol/l compared to cysteine product, 5 μm of ol/l cysteines obtain
Core shell structure the obvious step-down of circular dichroism optical activity, the circular dichroism activity of the core shell structure that 1 μm of ol/l cysteine obtains
Less than 5 μm of ol/l cysteines, and the core shell structure circular dichroism activity that 15 μm of ol/l cysteines obtain and 10 μm of ol/l half Guangs
The circular dichroism activity of the product that propylhomoserin obtains is more or less the same.And the product being obtained by the experiment condition of comparative example 5 no substantially justifies two
Color activity, illustrates for body series, and in chiral molecules, chiral molecules addition very little, is not enough to induce circular dichroism living source
Visible circular dichroism activity, and the inducing action of chiral molecules has saturation value, so 10 μm of ol/l cysteines are preferred value.
By the reaction condition of embodiment 9 and 10, the chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer obtaining
The shell thickness of material is less than embodiment 5, and this is to lead to because the amount of the tetraethyl orthosilicate of addition is less.
By the reaction condition of comparative example 7, due to the amount of tetraethyl orthosilicate that adds very little, be not enough to form shell it is impossible to
Obtain the chiral gold nanorods assembly product shoulder to shoulder of coated silica, and the reaction condition by comparative example 8, positive silicic acid second
The amount of ester is too many, the chiral gold nanorods of cladding shoulder to shoulder after assembly easily sedimentation it is impossible to obtain stable chiral gold nano
Rod assembly@silicon dixoide nucleocapsid structure nano material.
The product being obtained by the reaction condition of embodiment 11 is compared with embodiment 5, and silica shell thickness is less, and this is
Cause because the reaction time is shorter, and the product being obtained by the reaction condition of embodiment 12 and comparative example 10 and embodiment 5
The product arriving is similar to, and the silicon source for this concentration is described, 3h i.e. its hydrolysis enough forms stable dioxy on gold nanorods surface
SiClx shell structurre.And the reaction condition of comparative example 9 cannot obtain the chiral gold nanorods assembling of stable coated silica
Body product, this is because the reaction time is too short, and tetraethyl orthosilicate has little time to hydrolyze to form stable shell.
The circle two of the chiral gold nanosphere assembly silicon dixoide nucleocapsid structure nano material that Fig. 9 obtains for comparative example 11
Color spectrum, finds that the circular dichroism optical activity of the core shell structure that core is gold nanosphere is significantly less than chiral gold nano-rod assembly@
Silicon dixoide nucleocapsid structure nano material.This proves the necessity by the use of gold nanorods assembly as core further.
The chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nano material that Figure 10 obtains for embodiment 5 is in time
Change circular dichroism, find this composite preparation 6 months afterwards circular dichroism optical activity still can obtain
Keep.
In sum, the invention provides one kind has good stability and the optically active chiral gold of adjustable circular dichroism
Nano-rod assembly@silicon dixoide nucleocapsid structure nano material.By regulating and controlling the concentration of connection molecule sodium citrate, can regulate and control
The optical activity of this core shell structure.Compared with existing chiral gold nano-rod assembly nano material, the nucleocapsid of present invention preparation
Structure chiral gold nano-rod assembly nano material has fabulous stability, and the circular dichroism optics that simultaneously can keep stronger is lived
Property.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (17)
1. a kind of gold nanorods-silicon dixoide nucleocapsid structure nano material is it is characterised in that described core-shell structured nanomaterials
Nuclear structure is to have circular dichroism optically active chirality gold nanorods assembly shoulder to shoulder, and shell structure is silica；
The thickness of described shell structure silica is 20～50nm；
Described chirality gold nanorods are shoulder to shoulder in assembly, number >=2 of gold nanorods；
The draw ratio of described gold nanorods is 2～5:1；
The preparation method of described gold nanorods-silicon dixoide nucleocapsid structure nano material comprises the steps:
(1) prepare chiral gold nanorods assembly shoulder to shoulder；
(2) by chiral gold nanorods assembly coated silica shell in alcohol-water system shoulder to shoulder, obtain chiral gold nano
Rod assembly@silicon dixoide nucleocapsid structure nano material；
The step of step (2) described chirality gold nanorods assembly coated silica shell shoulder to shoulder is:
The chiral gold nanorods obtaining to step (1) add alcohol in the assembly aqueous solution shoulder to shoulder, adjust solution ph to 8～10,
Add tetraethyl orthosilicate, after stirring is reacted, obtain chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer material
Material；
The described alcohol of step (2) is the mixture of any a kind or at least 2 kinds in methyl alcohol, ethanol or isopropanol；
The addition of described alcohol and the volume ratio of the aqueous solution are 1:4；
In the gold nanorods aqueous solution of 1nmol/l, after described tetraethyl orthosilicate adds, in reaction solution, tetraethyl orthosilicate is dense
Spend for 5～9mmol/l；
The temperature of described reaction is 20～30 DEG C, and the time is 2～5h.
2. gold nanorods as claimed in claim 1-silicon dixoide nucleocapsid structure nano material is it is characterised in that described shell is tied
The thickness of structure silica is 30～40nm；
Described chirality gold nanorods are shoulder to shoulder in assembly, the number 3～10 of gold nanorods；
The draw ratio of described gold nanorods is 3～4:1.
3. a kind of preparation method of gold nanorods as claimed in claim 1 or 2-silicon dixoide nucleocapsid structure nano material, its
It is characterised by, methods described comprises the steps:
(1) prepare chiral gold nanorods assembly shoulder to shoulder；
(2) by chiral gold nanorods assembly coated silica shell in alcohol-water system shoulder to shoulder, obtain chiral gold nano
Rod assembly@silicon dixoide nucleocapsid structure nano material；
The step of step (2) described chirality gold nanorods assembly coated silica shell shoulder to shoulder is:
The chiral gold nanorods obtaining to step (1) add alcohol in the assembly aqueous solution shoulder to shoulder, adjust solution ph to 8～10,
Add tetraethyl orthosilicate, after stirring is reacted, obtain chiral gold nano-rod assembly@silicon dixoide nucleocapsid structure nanometer material
Material；
The described alcohol of step (2) is the mixture of any a kind or at least 2 kinds in methyl alcohol, ethanol or isopropanol；
The addition of described alcohol and the volume ratio of the aqueous solution are 1:4；
In the gold nanorods aqueous solution of 1nmol/l, after described tetraethyl orthosilicate adds, in reaction solution, tetraethyl orthosilicate is dense
Spend for 5～9mmol/l；
The temperature of described reaction is 20～30 DEG C, and the time is 2～5h.
4. method as claimed in claim 3 is it is characterised in that step (1) described chirality gold nanorods assembly shoulder to shoulder
Preparation process is:
Gold nanorods are dispersed in the aqueous solution containing cationic surfactant, add the chiral small molecule with sulfydryl afterwards
Form chiral gold nanorods assembly shoulder to shoulder with sodium citrate.
5. method as claimed in claim 4 it is characterised in that in step (1) aqueous solution gold nanorods concentration be 0.8～
1.2nmol/l.
6. method as claimed in claim 5 it is characterised in that in step (1) aqueous solution gold nanorods concentration be 1nmol/
l；
7. method as claimed in claim 4 is it is characterised in that in the gold nanorods aqueous solution of 1nmol/l, cationic surface
The concentration of activating agent is 0.4～1mmol/l, and the concentration of the chiral small molecule with sulfydryl is 1～10 μm of ol/l, sodium citrate dense
Spend for 20～50 μm of ol/l.
8. method as claimed in claim 4 is it is characterised in that in the gold nanorods aqueous solution of 1nmol/l, surface-active
The concentration of agent, the chiral small molecule with sulfydryl and sodium citrate is 0.5mmol/l, 10 μm of ol/l and 50 μm of ol/l.
9. method as claimed in claim 4 is it is characterised in that the draw ratio of described gold nanorods is 2～5:1.
10. method as claimed in claim 9 is it is characterised in that the draw ratio of described gold nanorods is 3～4:1.
11. methods as claimed in claim 4 are it is characterised in that described cationic surfactant is cetyl trimethyl
Ammonium bromide.
12. methods as claimed in claim 4 are it is characterised in that the described chiral small molecule containing sulfydryl is cysteine, reduction
The mixing of any a kind or at least 2 kinds in type paddy light ammonia peptide and n- acetylcysteine.
13. methods as claimed in claim 4 are it is characterised in that the described chiral small molecule containing sulfydryl is cysteine.
It is characterised in that the temperature of described reaction is 20～30 DEG C, the time is 3h to 14. methods as claimed in claim 3.
15. methods as claimed in claim 3 are it is characterised in that methods described comprises the steps:
(1) draw ratio is that 2～5:1 gold nanorods are dispersed in the aqueous solution containing cationic surfactant, adds afterwards
Chiral small molecule with sulfydryl and sodium citrate form chiral gold nanorods assembly shoulder to shoulder；Wherein, in the described aqueous solution, gold
The concentration of nanometer rods is 1nmol/l, and the concentration of surfactant is 500 μm of ol/l, and the concentration of the chiral small molecule with sulfydryl is
10 μm of ol/l, the concentration of sodium citrate is 50 μm of ol/l；
(2) add alcohol in the chiral gold nanorods that step (1) obtains shoulder to shoulder the assembly aqueous solution, make alcohol/water volume ratio control
System, in 1:4, adjusts solution ph to 9, adds tetraethyl orthosilicate, obtains chiral gold nano-rod assembly@titanium dioxide after stirring reaction
Silicon core-shell structured nanomaterials.
A kind of 16. purposes of gold nanorods as claimed in claim 1-silicon dixoide nucleocapsid structure nano material, its feature exists
In described gold nanorods-silicon dixoide nucleocapsid structure nano material is used as the enhancing substrate of chiral molecules.
17. purposes as claimed in claim 16 are it is characterised in that described gold nanorods-silicon dixoide nucleocapsid structure nanometer material
Expect the trace detection for chiral biomolecule and NO free radical.
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| CN106807940B (en) * | 2015-11-27 | 2019-08-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Colloidal gold/di-iron trioxide core-shell type nano structural composites and preparation method thereof |
| CN105817617B (en) * | 2016-05-24 | 2018-01-30 | 中国科学院理化技术研究所 | A kind of nano-hybrid material of gold nanorods/silicon/carbon dioxide point and its preparation method and application |
| CN106086793B (en) * | 2016-07-01 | 2018-09-04 | 陕西师范大学 | A kind of two dimension chiral metal-medium nanostructure and preparation method thereof |
| JP6923778B2 (en) * | 2017-02-10 | 2021-08-25 | 国立大学法人山梨大学 | Method for synthesizing silica-coated highly dispersible gold nanorods and dispersion of synthesized gold nanorods |
| WO2019194509A1 (en) * | 2018-04-06 | 2019-10-10 | 서울대학교산학협력단 | Three-dimensional chiral nanostructure |
| KR102173227B1 (en) | 2018-04-06 | 2020-11-03 | 서울대학교산학협력단 | Three dimensional chiral nanostructures |
| CN109698075B (en) * | 2018-06-29 | 2020-12-11 | 张贤芝 | Multi-core single-shell structure Au @ mSiO2Composite microsphere, preparation method and application |
| CN111112596B (en) * | 2018-11-01 | 2021-12-28 | 国家纳米科学中心 | Chiral noble metal nano-particles and preparation method and application thereof |
| CN109358195B (en) * | 2018-11-06 | 2022-04-26 | 枣庄学院 | Hollow gold platinum alloy nanocage core-porous silica shell nanoenzyme and preparation method and application thereof |
| CN112300778B (en) * | 2019-07-30 | 2023-11-03 | 国家纳米科学中心 | Circularly polarized luminescent material and preparation method and application thereof |
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