CN104897646B - A kind of Au@are combined Raman microprobe preparation method to sulfydryl benzenethiol@Au - Google Patents
A kind of Au@are combined Raman microprobe preparation method to sulfydryl benzenethiol@Au Download PDFInfo
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- CN104897646B CN104897646B CN201510362132.3A CN201510362132A CN104897646B CN 104897646 B CN104897646 B CN 104897646B CN 201510362132 A CN201510362132 A CN 201510362132A CN 104897646 B CN104897646 B CN 104897646B
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- sulfydryl
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Abstract
Raman microprobe and preparation method thereof is combined to sulfydryl benzenethiol@Au the invention discloses a kind of [email protected] compound Raman microprobe is made up of inner core nanogold particle, Raman molecular interlayer and outside golden shell layer, its preparation method is to add gold chloride in sodium citrate solution to prepare core nanogold, in core nanogold over-assemble to sulfydryl benzenethiol, golden shell layer is being prepared to sulfydryl benzenethiol surface again, Au@is being obtained and Raman microprobe is combined to sulfydryl benzenethiol@Au;Raman signal molecule is in the sandwich of layers between core nanogold and golden shell to sulfydryl benzenethiol in the Raman microprobe of preparation, is not affected by the surrounding environment, stability is good;The gold surface chemical property of probe is homogeneous, can modify various biomolecule, therefore available for the detection of a variety of biomarkers, it is applied widely.
Description
Technical field
The present invention relates to the preparation method that a kind of Au@are combined Raman microprobe to sulfydryl benzenethiol@Au;Belong to biological nano neck
Domain.
Background technology
Cancer has become one of major disease of 21st century threat human health.Therefore, cancer markers content
Accurate detection turn into urgent problem to be solved.Golden nanometer particle is applied to amplify Raman signal in Raman detection, it is real
The Sensitive Detection of existing cancer markers.But, directly in nanogold surface modification Raman molecular, centrifugation in subsequent experimental,
In the operation such as washing, Raman molecular easily loses or is denatured so that the sensitivity and the degree of accuracy of detection are affected.Therefore, solve
The defect that certainly existing decorated by nano-gold Raman molecular is present, is the key technology that it can further develop.
The content of the invention
The defect existed for existing nanogold surface modification Raman molecular, the purpose of the present invention is to be to provide a kind of
Signal is strong, be easy to modified biological molecule, and the good Au@of stability are combined Raman microprobe to sulfydryl benzenethiol@Au.
Another object of the present invention be provide one kind by simple operations, prepare the Au@in a mild condition
The method of Raman microprobe is combined to sulfydryl benzenethiol@Au.
In order to realize the technical purpose of the present invention, Raman is combined to sulfydryl benzenethiol@Au the invention provides a kind of Au@and visited
Pin, the Au@are combined Raman microprobe to sulfydryl benzenethiol@Au by inner core nanogold particle, Raman molecular interlayer and outside golden shell
Layer is constituted.
Technical scheme will be set to the inside interlayer of nanogold to sulfydryl benzenethiol Raman molecular first, build
Go out interlayer structures of the Au@to sulfydryl benzenethiol@Au, by the golden shell layer of outside cladding, make steady to sulfydryl benzenethiol physico-chemical property
Fixed, resistance to ambient influnence ability is strong, and maintains the strong advantage of Raman molecular signal, while golden shell surface is easy to modified biological point
Son.Technical scheme efficiently solve existing decorated by nano-gold Raman molecular in detection process easily loss or
Denaturation, causes the sensitivity of detection and the defect of accuracy.
It is preferred that scheme center nanogold particle average grain diameter be 42~48nm.
It is preferred that scheme in Raman molecular thickness of interlayer be 2~4nm.
It is preferred that scheme in golden shell thickness be 3~8nm.It is preferred that the golden shell of suitable thickness is more beneficial for protecting Raman molecular
Stability, while not influenceing signal intensity.
It is preferred that scheme in Raman molecular be to sulfydryl benzenethiol.
The method that the Au@are combined Raman microprobe to sulfydryl benzenethiol@Au, this method are prepared present invention also offers a kind of
It is that chlorauric acid solution is added to the solution that reaction in sodium citrate solution obtains the nanogold particle containing core, in nanogold containing core
Added in the solution of grain and sulfydryl benzenethiol is reacted, obtain Au@to sulfydryl benzenethiol;Gained Au@are to sulfydryl benzenethiol by dividing
After being dispersed in sodium citrate solution, gold chloride reaction is added, Au@is produced and Raman microprobe is combined to sulfydryl benzenethiol@Au.
The Au@that prepare of the present invention are combined the method for Raman microprobe to sulfydryl benzenethiol@Au also including following preferred scheme:
It is preferred that scheme in chlorauric acid solution is gradually added into excessive sodium citrate solution, maintain temperature 82~
Reacted under the conditions of 93 DEG C, obtain the solution of the nanogold particle containing core.
More preferably the solution of the nanogold particle containing core is prepared via a method which to obtain in scheme:By chlorauric acid solution plus
Enter into the sodium citrate solution of boiling, react under reflux conditions after 30~40min, be cooled to 82~93 DEG C, then add portion
Divide chlorauric acid solution, continue to react 25~35min, then add part chlorauric acid solution, further react after 25~35min, it is cold
But to room temperature;Sodium citrate solution and water are added in the solution of cooling, when being warming up to 82~93 DEG C, addition part gold chloride is molten
Liquid, reacts 25~35min, then adds part chlorauric acid solution, continues to react 25~35min, is cooled to room temperature, produces.
It is preferred that scheme in added in the solution of the nanogold particle containing core it is excessive to sulfydryl benzenethiol, in stirring condition
Under, 3~5h is reacted, is centrifuged, solid product is washed, removes excessive to sulfydryl benzenethiol, Au@are obtained to sulfydryl benzene sulphur
Alcohol.
It is preferred that scheme in Au@are dispersed in Na to sulfydryl benzenethiol3C6H5O7After in solution, 82~93 DEG C are heated to, plus
Enter chlorauric acid solution stirring reaction, obtain Au@and Raman microprobe is combined to sulfydryl benzenethiol@Au.
It is preferred that scheme comprise the following steps:
Step one:Prepare the solution of the nanogold particle containing core
The chlorauric acid solution for being 22~28mM by 0.8~1.2mL concentration be added to 140~160mL concentration be 2.0~
In 2.4mM sodium citrate solution, under reflux conditions after stirring reaction to colour stable, continue 25~35min of stirring reaction,
Be cooled to 82~93 DEG C, then add the chlorauric acid solution that 0.8~1.2mL concentration is 22~28mM, continue stirring reaction 25~
35min, then add after the chlorauric acid solution that 0.8~1.2mL concentration is 22~28mM, further 25~35min of stirring reaction, stir
Mix and be cooled to room temperature;The solution for taking 50~60mL to cool down, adds the sodium citrate solution that 1.5~2.5mL concentration is 55~65mM
With 50~60mL water, when being warming up to 82~93 DEG C, 0.8~1.2mL of addition concentration is 22~28mM chlorauric acid solutions, stirring reaction
25~35min, then 0.8~1.2mL concentration is added for 22~28mM chlorauric acid solutions, 25~35min of stirring reaction, stirring cooling
To room temperature, the solution of the nanogold particle containing core is produced;
Step 2:Au@are prepared to sulfydryl benzenethiol
It is 0.8 to add 0.8~1.2mL concentration in the solution of the one obtained nanogold particle containing core the step of 8~12mL
×10-4~1.2 × 10-4M to sulfydryl benzenethiol solution, 3~5h is reacted under agitation, is centrifuged, washing solid production
Thing, removes excessive to sulfydryl benzenethiol, obtains Au@to sulfydryl benzenethiol;
Step 3:Prepare Au@and Raman microprobe is combined to sulfydryl benzenethiol@Au
Au@obtained by step 2 are diluted to 8 for 1.8~2.4mM sodium citrate solution to sulfydryl benzenethiol with concentration~
12mL, takes 5.0~6.0mL dilutions, further with the sodium citrate solution and 5.0 that 0.15~0.25mL concentration is 55~65mM
After the dilution of~6.0mL water, 82~93 DEG C are heated to, 80~120 μ L concentration is added and is reacted for 20~30mM chlorauric acid solution, instead
Answer after 25~35min, be cooled to room temperature, produce Au@and Raman microprobe is combined to sulfydryl benzenethiol@Au.
In currently preferred technical scheme, by the concentration, the reaction that adjust chlorauric acid solution and sodium citrate solution
The condition such as temperature and reaction cycle number of times can control well core nano Au particle pattern and size and golden shell layer
Thickness.By the Raman molecular for adding excessive Raman molecular can be made preferably to coat core nanogold, improve Au well to mercapto
Base benzenethiol@Au are combined Raman microprobe signal intensity.
Compared with the prior art, the advantageous effects that technical scheme is brought:
1) Au@of the invention are combined Raman microprobe to sulfydryl benzenethiol@Au by preparing uniform outer layer golden shell, can be very
Well with biomolecule (such as:Cancer markers) connection;
2) Au@of the invention are carried to the sulfydryl benzenethiol@Au core nano-particles being combined inside Raman microprobe for Raman molecular
For rough surface, it is easy to amplify Raman signal;
3) Au@of the invention are combined Raman microprobe to sulfydryl benzenethiol@Au, and with interlayer structure, Raman molecular is in golden shell
Protection under, property is stable, favorable reproducibility, and resistance to ambient influnence ability is strong, efficiently solves existing decorated by nano-gold Raman point
Son easily loss or denaturation in detection process, causes the sensitivity of detection and the defect of accuracy.
Brief description of the drawings
【Fig. 1】The preparation process schematic diagram of Raman microprobe is combined to sulfydryl benzenethiol@Au for Au@;
【Fig. 2】For the transmission electron microscope figure of core nano Au particle;
【Fig. 3】The transmission electron microscope figure of Raman microprobe is combined to sulfydryl benzenethiol@Au for Au@;
【Fig. 4】For Au NPs, Au@to sulfydryl benzenethiol, Au@to sulfydryl benzenethiol@Au grain-size graph;
【Fig. 5】For Au@to sulfydryl benzenethiol, Au@to sulfydryl benzenethiol@Au Raman figure.
【Fig. 6】It is used for the Raman figure that human serum and various concentrations free-PSA antigen are detected to be combined Raman microprobe.
Embodiment
Following examples are intended to further illustrate present invention, rather than to the limit of the claims in the present invention protection domain
System.
Embodiment 1
The preparation of core nano Au particle.
Step is as follows:150mL 2.2mM Na are added in 250mL three-necked flask3C6H5O7, in stirring (1500r
min-1), boiling is heated in the presence of condensing reflux, add 1mL 25mM HAuCl4, solution colour reddens and stably after 10min,
After 30min, cool the temperature to 90 DEG C (being denoted as g0), add 1mL 25mM HAuCl4, react 30min;1mL 25mM are added again
HAuCl4, react after 30min, stirring is cooled to room temperature (being denoted as g1).
55mL above-mentioned solution is taken, 2mL 60mM Na is added3C6H5O7, 53mL ultra-pure waters are added, 90 DEG C, weight are warming up to
Multiple g1 operation is once.Produce the solution (being denoted as g2) of the nanogold containing core.Shown in the shape appearance figure 2 of core nanogold, Fig. 2 can be seen that
Nano-particle is evengranular spherical.
Preparations of the Au@to sulfydryl benzenethiol.
Step is as follows:
1mL 10 is added in the solution of 10mL core nanogold-4M to sulfydryl benzenethiol, the lower reaction 4h of stirring, centrifugation,
Siphon away after supernatant, wash solid product, remove excessive to sulfydryl benzenethiol, produce Au@to sulfydryl benzenethiol.
Preparations of the Au@to sulfydryl benzenethiol@Au.
Step is as follows:
It is 2.2mM Na with concentration to sulfydryl benzenethiol by Au@3C6H5O7Solution is diluted to 10mL, produces Au@to sulfydryl benzene
Mercaptan citric acid solution, takes 5.5mL Au@to sulfydryl benzenethiol citric acid solution, the sodium citrate for adding 0.2mL 60mM is molten
Liquid, adds after the dilution of 5.3mL ultra-pure waters, is heated to 90 DEG C, 100 μ L 25mM HAuCl are added thereto4, react cold after 30min
But to room temperature, Au@are produced Raman microprobe is combined to sulfydryl [email protected]@to shown in sulfydryl benzenethiol@Au shape appearance figure 3,
Fig. 3 can be seen that nano-particle is evengranular spherical.
Core nano Au particle, Au@are combined the particle diameter point of Raman microprobe to sulfydryl benzenethiol and Au@to sulfydryl benzenethiol@Au
Cloth is as shown in figure 4, Fig. 4 can be seen that from Au NPs to Au@to sulfydryl benzenethiol, then to Au@to sulfydryl benzenethiol@Au, particle diameter
In increase, illustrate to have modified successively in core nanogold to sulfydryl benzenethiol and golden shell layer, be built into interlayer structure.
Fig. 5 can be seen that the Raman signal that Au@are combined Raman microprobe to sulfydryl benzenethiol@Au is still very strong.
Fig. 6 can be seen that compound Raman microprobe only has response to free-PSA antigen, and with free-PSA
The increase Raman signal of antigen concentration is in enhancing.
Au@are combined the sign of Raman microprobe to sulfydryl benzenethiol@Au, and step is as follows:
(1) sample of transmission electron microscope:Take 10 μ L Au NPs drops in copper mesh, survey transmission electron microscope is made
Sample;
(2) sample of particle diameter:1mL Au NPs, Au@is taken to add sulfydryl benzenethiol, Au@to sulfydryl benzenethiol@Au respectively
1mL particle diameter sample cell surveys particle diameter;
(3) sample 1 of Raman:Take 10 μ L Au@to sulfydryl benzenethiol, Au@to sulfydryl benzenethiol respectively
@Au are dropped in golden film, are dried naturally.
(4) sample 2 of Raman:Golden film is activated (MUA, EDC/NHS) first, the μ g/mL of 40 μ L 10 capture antibody is instilled
Anti-PSA McAb, are respectively dropped into the free-PSA antigen of 40 μ L human serums and various concentrations, instill 40 μ L anti-
Free PSA McAb (need cleaning, remove uncombined material) before being added dropwise every time.
Claims (1)
1. a kind of Au@are combined the preparation method of Raman microprobe to sulfydryl benzenethiol@Au, it is characterised in that the Au@are to sulfydryl benzene
Mercaptan@Au are combined Raman microprobe and are made up of inner core nanogold particle, Raman molecular interlayer and outside golden shell layer;
Described core nanogold particle average grain diameter is 42~48nm;Described Raman molecular thickness of interlayer is 2~4nm;It is described
Golden shell thickness be 3~8nm;
The Au@are combined the preparation method of Raman microprobe to sulfydryl benzenethiol@Au, comprise the following steps:
Step one:Prepare the solution of the nanogold particle containing core
It is 2.0~2.4mM's that the chlorauric acid solution for being 22~28mM by 0.8~1.2mL concentration, which is added to 140~160mL concentration,
In sodium citrate solution, under reflux conditions after stirring reaction to colour stable, continue 25~35min of stirring reaction, be cooled to
82~93 DEG C, then the chlorauric acid solution that 0.8~1.2mL concentration is 22~28mM is added, continue 25~35min of stirring reaction, then
Add after the chlorauric acid solution that 0.8~1.2mL concentration is 22~28mM, further 25~35min of stirring reaction, stirring is cooled to
Room temperature;Take 50~60mL cool down solution, add 1.5~2.5mL concentration be 55~65mM sodium citrate solution and 50~
60mL water, when being warming up to 82~93 DEG C, adds 0.8~1.2mL concentration for 22~28mM chlorauric acid solutions, and stirring reaction 25~
35min, then 0.8~1.2mL concentration is added for 22~28mM chlorauric acid solutions, 25~35min of stirring reaction, stirring is cooled to room
Temperature, produces the solution of the nanogold particle containing core;
Step 2:Au@are prepared to sulfydryl benzenethiol
It is 0.8 × 10 to add 0.8~1.2mL concentration in the solution of the one obtained nanogold particle containing core the step of 8~12mL-4
~1.2 × 10-4M to sulfydryl benzenethiol solution, 3~5h is reacted under agitation, is centrifuged, solid product is washed, removes
Go excessive to sulfydryl benzenethiol, obtain Au@to sulfydryl benzenethiol;
Step 3:Prepare Au@and Raman microprobe is combined to sulfydryl benzenethiol@Au
Au@obtained by step 2 are diluted to 8~12mL with concentration to sulfydryl benzenethiol for 1.8~2.4mM sodium citrate solution,
Take 5.0~6.0mL dilutions, further with 0.15~0.25mL concentration for 55~65mM sodium citrate solution and 5.0~
After the dilution of 6.0mL water, 82~93 DEG C are heated to, 80~120 μ L concentration is added and is reacted for 20~30mM chlorauric acid solution, reaction
After 25~35min, room temperature is cooled to, Au@is produced and Raman microprobe is combined to sulfydryl benzenethiol@Au.
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