CN107158381A - A kind of preparation method and applications of the gold nano star@copper sulfide photo-thermal probes with photo-thermal enhancement effect - Google Patents
A kind of preparation method and applications of the gold nano star@copper sulfide photo-thermal probes with photo-thermal enhancement effect Download PDFInfo
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- CN107158381A CN107158381A CN201710355513.8A CN201710355513A CN107158381A CN 107158381 A CN107158381 A CN 107158381A CN 201710355513 A CN201710355513 A CN 201710355513A CN 107158381 A CN107158381 A CN 107158381A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
- A61K49/0067—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle quantum dots, fluorescent nanocrystals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0069—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the agent being in a particular physical galenical form
- A61K49/0089—Particulate, powder, adsorbate, bead, sphere
- A61K49/0091—Microparticle, microcapsule, microbubble, microsphere, microbead, i.e. having a size or diameter higher or equal to 1 micrometer
- A61K49/0093—Nanoparticle, nanocapsule, nanobubble, nanosphere, nanobead, i.e. having a size or diameter smaller than 1 micrometer, e.g. polymeric nanoparticle
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of preparation method of the gold nano star@copper sulfide photo-thermal probes with photo-thermal enhancement effect, it the described method comprises the following steps：Small gold nano grain is prepared first with hydrothermal method, surface modification is carried out with cetyl ammonium bromide to small gold nano grain；Thiobenzoate nickel and mantoquita are added in the small gold nano grain that cetyl ammonium bromide is modified, mixed solution is then subjected to high-temperature process, small gold grain@copper sulfide particles are obtained；Then using small gold grain copper sulfide particles as seed crystal, gold nano star is prepared by seeded growth method and vulcanizes copper compound structure；It is last to carry out the modification of crosslinking agent in composite structure surface to facilitate the various biomolecule of link, obtain gold nano star@copper sulfide photo-thermal probes.Relative to traditional probe, this probe is the enhanced photo-thermal probe of photo-thermal, can effectively orient kill cancer cell, and the photothermal deformation effect of copper sulfide itself is enhanced, and additionally improves the biocompatibility of copper sulfide.
Description
Technical field
The present invention relates to nano-probe technical field, it is prepared for using seeded growth method and Heteroepitaxy method a kind of with light
The gold nano star@copper sulfide photo-thermal probes of hot enhancement effect, realize the targeting photo-thermal therapy to cancer cell.
Background technology
Cancer is still to threaten maximum and most one of disease of challenge.According to statistics, about 7,600,000 people in 2008 die from cancer
Disease, this numeral is in the year two thousand thirty it is expected that be up to 13,100,000, and the struggle of the mankind and cancer is also shouldered heavy responsibilities.In recent years, nanometer material
The photo-thermal therapy of material is a study hotspot in biomedical sector, and so-called photo-thermal therapy refers to utilize the strong of nano material
Sink effect, heat energy or phonon are converted to by the photon energy in incident light, localized hyperthermia are produced, so as to kill the cancer around it
Cell, reaches the purpose for the treatment of of cancer.Copper sulfide (CuS) nano material, as emerging photo-thermal therapy material, is a kind of p-type half
Conductor material, with good electrical and optical properties, in fields such as photo-thermal therapy, drug delivery, sensor, molecular imagings
It is widely used.It is advantageous that:On the one hand, CuS is as a kind of semiconductor nanoparticle, with preparation technology it is simple,
Particle size is smaller, cheap, the more low internal characteristicses of toxicity, is highly suitable for the research and application of biomedical sector；
On the other hand, the optical absorption characteristic of nano copper sulfate particle concentrates near infrared light (700-1100nm) wave band, photo-thermal therapy
During the near infrared light light source exactly stronger to biological tissue's penetration capacity that uses, can effectively reduce biological tissue to light
Absorption, simultaneously because d-d energy level transition of the absorption characteristic of CuS materials inside its copper ion between band gap, it absorbs
Wave band is not disturbed by extraneous medium substantially, improves its optical stability.Based on two above reason, CuS nano particle quilts
It is considered as one of nanometer optothermal material of most prospect.In recent years, copper sulfide is so that its preparation technology is simple, particle size is small, price
Cheap, low toxin is considered as the first choice of preferable photo-thermal probe by scientific research personnel, but the photothermal deformation of copper sulphide material
One piece of worry of the relatively relatively low always scientific research personnel of efficiency.
The content of the invention
In order to improve the photo-thermal conversion efficiency of copper sulfide nano material, the composite construction of nano metal and copper sulfide is prepared,
Realized present invention utilizes the local surface plasma resonance of nano metal (LSPR) effect to copper sulfide photo-thermal conversion efficiency
Raising.Based on this, the first object of the present invention is to provide a kind of gold nano star vulcanization bronzing with photo-thermal enhancement effect
The preparation method of thermal probe.
Another object of the present invention is to provide the photo-thermal probe of methods described preparation.
The a further object of the present invention is to provide application of the probe of the preparation method and its preparation in oncotherapy.
The photo-thermal probe of gold nano star@copper sulfides is prepared for by liquid phase process in the present invention, based on gold nano star
Local surface plasma resonance effect strengthens the photo-thermal conversion efficiency of copper sulfide, reaches the purpose of enhancing photo-thermal therapy.It is compound
Strong sink effect of the photo-thermal probe based on nano particle can realize the photo-thermal therapy of cancer cell.Utilize the life of gold nano star well
Thing characteristic improves the biocompatibility of combined probe.
The present invention prepares gold nano star copper sulfide photo-thermal probe using seeded growth method with Heteroepitaxy method.First with
Hydrothermal method prepares small gold nano grain, and surface modification is carried out with cetyl ammonium bromide to small gold nano grain；In hexadecane
Thiobenzoate nickel and mantoquita are added in the small gold nano grain of base ammonium bromide modification, then carries out mixed solution at high temperature
Reason, obtains gold grain@copper sulfide particles；Then using gold grain copper sulfide particles as seed crystal, Jenner is prepared by seeded growth method
Rice star vulcanization copper compound structure；It is last to carry out the modification of crosslinking agent in composite structure surface to facilitate the various biomolecule of link,
Obtain gold nano star@copper sulfide photo-thermal probes.
Specifically, method of the invention comprises the following steps：
(1) preparation of small gold nano grain@copper sulfides:
The lemon that 0.1mL-50mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to 50mL mass fractions
Sour sodium (or sodium borohydride, ascorbic acid, THPC) solution, after reacting 10-360 minutes, obtains small gold nano
Grain；10mL concentration is added into reaction solution to be modified for 0.5M CTAB (cetyl ammonium bromide)；Then by thio phenyl
Nickel formate and mantoquita are added in small gold nano grain, and then this mixture is put into autoclave, carry out 100-300 degrees Celsius
The small gold nano grain@copper sulfide particles of preparation are carried out centrifuge washing, are dissolved in 20mL high purity waters by reaction 1 to 96 hour；
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials4Small gold nano grain@sulphur obtained by the step of middle addition 4mL (1)
Change and stirred 5 minutes after copper particle, 50uL HCl solutions are mixed with the solution；Then silver nitrate and 0.025mol Vitamin C are added
Acid, reaction is standby after being centrifuged after 1 minute；
(3) preparation of gold nano star@copper sulfide photo-thermal probes：
Cross-linking reaction is carried out using the modification group and various biomolecules of gold nano star@copper sulfide composite structure surfaces,
Obtain gold nano star@copper sulfide photo-thermal probes.
It is preferred that, during the small gold nano grain is gold nanosphere, gold nanorods, gold nano cube, golden polygon
Any one.
It is preferred that, thiobenzoate nickel described in step (1) is 1 with gold chloride mol ratio:0.1 to 1:2；The mantoquita with
The mol ratio of thiobenzoate nickel is 1:0.3 to 1:10, mantoquita can be copper chloride, copper sulphate, copper nitrate.
It is preferred that, the mol ratio of silver nitrate and gold chloride described in step (2) is 1：10 to 1：40.
It is preferred that, the modification group includes amino group, carboxylic group etc.；The biomolecule includes antibody, DNA pieces
Section and any one in bio-ligand.
Further, the invention provides gold nano star@copper sulfide photo-thermal probe photo-thermal probes prepared by methods described.
Further, orient and follow the trail of in cancer cell the invention provides the gold nano star@copper sulfides photo-thermal probe, cancer
Application in the photo-thermal therapy of cell.The cancer cell includes all malignant cells such as breast cancer cell etc..
Beneficial effect
Relative to traditional probe, this probe is the enhanced photo-thermal probe of photo-thermal, can effectively orient kill cancer thin
Born of the same parents, the photothermal deformation effect of copper sulfide itself is enhanced, and additionally improves the biocompatibility of copper sulfide.
(1) using the surface plasma bulk effect of gold nano star, the raising to copper sulfide photothermal deformation effect is realized, is compared
In single copper sulfide and gold nano star, the light absorption effect of combined probe is enhanced.
(2) in combined probe, based on the good biological nature of gold nano grain, the bio-compatible of combined probe is improved
Property.
Brief description of the drawings
The application schematic diagram of Fig. 1 gold nano star@copper sulfide probes；
The transmission electron microscope picture of Fig. 2 gold nano star copper sulfide combined probes；
Fig. 3 combined probes and individual curing copper, the absorption spectrum of gold nano star；
Photo-thermal curative effect of Fig. 4 gold nano star@copper sulfides photo-thermal probes to breast cancer cell；
Fig. 5 is the abosrption spectrogram for the combined probe that six embodiments are obtained；
Fig. 6 is the heating curve figure for the combined probe that six embodiments are obtained.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.Unless otherwise specified, embodiment
In the conventional meanses that are well known to those skilled in the art of used technological means.
In embodiment reagent used can market be commercially available.
Ya Fu producers：Give an experimental instruments and equipment limited, model in Shanghai：100mL, operating temperature：≤ 220 degrees Celsius, work
Make pressure：≤3MPa.
Embodiment 1：
(1) preparation of small gold nano grain@copper sulfides:
The sodium citrate that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials molten
Liquid, reaction obtains small gold nano grain after 20 minutes, and the CTAB that 10mL concentration is 0.5M is added into reaction solution, then will
0.008mmol thiobenzoate nickel and 0.003mmol copper chloride are added in small gold nano grain, then by this mixture
It is put into autoclave, carries out 135 degrees Celsius and react 2 hours.Small gold nano grain@copper sulfide particles progress centrifugation to preparation is washed
Wash, be dissolved in 20mL high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.0005mmol silver nitrate and 0.025mol ascorbic acid, instead
Answer standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (antibody).Under 37 degree of environment, 0.05mmol antibody molecule is added to 0.005mmol composite construction
In, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally under the effect of extraneous light field, realized thin to cancer
The fluorescence labeling and photo-thermal therapy of born of the same parents.
Gold nano star@copper sulfide photo-thermal probe structural representations prepared by the present invention are as shown in Figure 1；In figure：Black main body
Part represents copper sulfide, and starlike gray portion represents gold nano star, and outside curve represents functional group.
The transmission electron microscope picture of gold nano star copper sulfide combined probe is as shown in Figure 2.The physics of gold nano star and copper sulfide
Characteristic is different, and the gray scale shown in transmission electron microscope is otherwise varied, and pitch black color part is gold nano star, light grey color part in figure
It is nano copper sulfate particle, as can be seen from the figure combined probe is dimerous by gold nano star and copper sulfide, is combined
Probe realizes both effective combinations.
Combined probe and individual curing copper, the absorption spectrum of gold nano star from figure as shown in figure 3, can take a fancy to compound spy
The absorption intensity of pin will be considerably better than the two mixture and individual curing copper, gold nano star, especially be more than 800 nanometers in wavelength
When.By measuring the absorption area of absorption line, the absorption intensity that can obtain combined probe is the 3.7 of simple copper sulfide probe
Times.
The photo-thermal of combined probe and copper sulfide kills cancer cell overall contrast figure as shown in figure 4, a figures are the photo-thermal of copper sulfide
Effect, b illustrates the photo-thermal effect of combined probe.It can be seen that the situation that combined probe kills cancer cell is significantly better than sulphur from figure
Change the photo-thermal effect of copper.
Embodiment 2：
(1) preparation of small gold nano grain@copper sulfides:
The sodium borohydride that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials molten
Liquid, reaction obtains small gold nano grain after 20 minutes, and the CTAB that 10mL concentration is 0.5M is added into reaction solution, then will
0.0015mmol thiobenzoate nickel and 0.003mmol copper chloride are added in small gold nano grain, are then mixed this
Thing is put into autoclave, is carried out 135 degrees Celsius and is reacted 2 hours.The small gold nano grain@copper sulfide particles of preparation are centrifuged
Washing, is dissolved in 20mL high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.0005mmol silver nitrate and 0.025mol ascorbic acid, instead
Answer standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (antibody).Under 37 degree of environment, 0.05mmol antibody molecule is added to 0.005mmol composite construction
In, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally under the effect of extraneous light field, realized thin to cancer
The fluorescence labeling and photo-thermal therapy of born of the same parents.
Embodiment 3：
(1) preparation of small gold nano grain@copper sulfides:
The tetra methylol chlorine that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials
Change phosphorus solution, reaction obtains small gold nano grain after 20 minutes, the CTAB that 10mL concentration is 0.5M is added into reaction solution, so
The copper chloride of 0.03mmol thiobenzoate nickel and 0.003mmol is added in small gold nano grain afterwards, then this is mixed
Compound is put into autoclave, is carried out 135 degrees Celsius and is reacted 2 hours.The small gold nano grain@copper sulfide particles of preparation are carried out from
The heart is washed, and is dissolved in 20mL high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.0005mmol silver nitrate and 0.025mol ascorbic acid, instead
Answer standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (such as antibody).Under 37 degree of environment, 0.05mmol antibody molecule is added to 0.005mmol composite construction
In, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally under the effect of extraneous light field, realized thin to cancer
The fluorescence labeling and photo-thermal therapy of born of the same parents.
Embodiment 4：
(1) preparation of small gold nano grain@copper sulfides:
The ascorbic acid that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials molten
Liquid, reaction obtains small gold nano grain after 20 minutes, and the CTAB that 10mL concentration is 0.5M is added into reaction solution, then will
0.008mmol thiobenzoate nickel and 0.003mmol copper chloride are added in small gold nano grain, then by this mixture
It is put into autoclave, carries out 135 degrees Celsius and react 2 hours.Small gold nano grain@copper sulfide particles progress centrifugation to preparation is washed
Wash, be dissolved in 20ml high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.0001mmol silver nitrate and 0.025mol ascorbic acid, instead
Answer standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (such as antibody).Under 37 degree of environment, 0.05mmol antibody molecule is added to 0.005mmol composite construction
In, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally under the effect of extraneous light field, realized thin to cancer
The fluorescence labeling and photo-thermal therapy of born of the same parents.
Embodiment 5：
(1) preparation of small gold nano grain@copper sulfides:
The sodium citrate that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials molten
Liquid, reaction obtains small gold nano grain after 20 minutes, and the CTAB that 10mL concentration is 0.5M is added into reaction solution, then will
0.008mmol thiobenzoate nickel and 0.003mmol copper chloride are added in small gold nano grain, then by this mixture
It is put into autoclave, carries out 135 degrees Celsius and react 2 hours.Small gold nano grain@copper sulfide particles progress centrifugation to preparation is washed
Wash, be dissolved in 20ml high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.001mmol silver nitrate and 0.025mol ascorbic acid, reaction
It is standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (such as antibody, DNA fragmentation, bio-ligand).Under 37 degree of environment, 0.05mmol antibody molecule is added to
In 0.005mmol composite construction, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally in ambient light
Under field action, the fluorescence labeling and photo-thermal therapy to cancer cell are realized.
Embodiment 6：
(1) preparation of small gold nano grain@copper sulfides:
The tetra methylol chlorine that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials
Change phosphorus solution, reaction obtains small gold nano grain after 20 minutes, the CTAB that 10mL concentration is 0.5M is added into reaction solution, so
The copper chloride of 0.008mmol thiobenzoate nickel and 0.003mmol is added in small gold nano grain afterwards, then this is mixed
Compound is put into autoclave, is carried out 135 degrees Celsius and is reacted 2 hours.The small gold nano grain@copper sulfide particles of preparation are carried out from
The heart is washed, and is dissolved in 20ml high purity waters.
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials44mL small gold nano is added in (being mixed with 50uL HCl solutions)
Stirred after particle@copper sulfide particles 5 minutes, then add 0.002mmol silver nitrate and 0.025mol ascorbic acid, reaction
It is standby after being centrifuged after 1 minute.
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Reaction can be crosslinked using the amino group of composite structure surface, carboxylic group, so as to realize to a variety of lifes
The link of thing molecule (such as antibody).Under 37 degree of environment, 0.05mmol antibody molecule is added to 0.005mmol composite construction
In, crosslinking 4 hours is then carried out under 37 degree, washing centrifugation is then carried out, finally under the effect of extraneous light field, realized thin to cancer
The fluorescence labeling and photo-thermal therapy of born of the same parents.
Application examples
The present invention has done the situation analysis that photo-thermal kills cancer cell for the obtained combined probe of 6 embodiments.Cancer is thin
Born of the same parents are human breast cancer cell MDA-MB-231 (commercially available).
The killing test of breast cancer cell MDA-MB-231 cells：By on breast cancer cell growth to 96 well culture plates, so
Grown 24 hours under 37 degree afterwards, then culture medium is flushed three times with PBS, then biomolecule will be connected with (such as
Antibody) combined probe and 1.9mL DMEM (dulbecco's modified eagle medium) be added in culture medium,
When culture medium cultivated under 37 degree 4 it is small when after, culture medium is rinsed with PBS three times it is not connected compound to remove
Probe.Photo-thermal effect research is finally carried out, the wavelength of laser used is 808nm, and power is 2W/cm2.For in culture medium
After cancer cell irradiates 10 minutes, cell is dyed and (uses double-colored kit, orange red to represent dead cell, green, which is represented, lives
Cell), and observed in Austria under Paasche microscope and shoot cell image.Specifically as shown in figure 4, being become clear in b pictures
There are a large amount of fragments (the really fragment of cell membrane) to represent cell apoptosis around position, and cells survival shape is represented without fragment
Condition is good).
As shown in figure 5, the absorption characteristic of embodiment 1 is most strong as we can see from the figure.As shown in fig. 6, can from figure
To see that the heating curve of embodiment 1 is most strong.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of the gold nano star@copper sulfide photo-thermal probes with photo-thermal enhancement effect, it is characterised in that described
Method comprises the following steps：
Small gold nano grain is prepared first with hydrothermal method, carrying out surface with cetyl ammonium bromide to small gold nano grain repaiies
Decorations；Thiobenzoate nickel and mantoquita are added in the small gold nano grain that cetyl ammonium bromide is modified, then by mixed solution
High-temperature process is carried out, small gold grain@copper sulfide particles are obtained；Then using small gold grain@copper sulfide particles as seed crystal, seed crystal is passed through
Growth method prepares gold nano star vulcanization copper compound structure；It is last to carry out the modification of crosslinking agent to facilitate chain in composite structure surface
Various biomolecule are connect, gold nano star@copper sulfide photo-thermal probes are obtained.
2. the method as described in claim 1, it is characterised in that methods described includes step in detail below：
(1) preparation of small gold nano grain@copper sulfides:
The sodium citrate that 0.1mL-50mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to 50mL mass fractions
Solution, after reacting 10-360 minutes, obtains small gold nano grain；10mL concentration is added into reaction solution to carry out for 0.5M CTAB
Modification；Then thiobenzoate nickel and mantoquita are added in small gold nano grain, then this mixture are put into autoclave,
Carry out 100-300 degrees Celsius to react 1 to 96 hour, centrifuge washing is carried out to the small gold nano grain@copper sulfide particles of preparation, it is molten
Solution is in 20mL high purity waters；
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials4Small gold nano grain@copper sulfides obtained by the step of middle addition 4mL (1)
Stirred 5 minutes after particle, 50uL HCl solutions are mixed with the solution；Then silver nitrate and 0.025mol ascorbic acid are added,
Reaction is standby after being centrifuged after 1 minute；
(3) preparation of gold nano star@copper sulfide photo-thermal probes
Cross-linking reaction is carried out using the modification group and various biomolecules of gold nano star@copper sulfide composite structure surfaces, obtains golden
Nanometer star@copper sulfide photo-thermal probes.
3. method as claimed in claim 2, it is characterised in that the small gold nano grain is gold nanosphere, gold nanorods, gold
Any one in nanocube, golden polygon.
4. method as claimed in claim 2, it is characterised in that thiobenzoate nickel described in step (1) and gold chloride mole
Than for 1:0.1 to 1:2；The mol ratio of the mantoquita and thiobenzoate nickel is 1:0.3 to 1:10, mantoquita can be copper chloride,
Copper sulphate or copper nitrate.
5. method as claimed in claim 2, it is characterised in that the mol ratio of silver nitrate and gold chloride is described in step (2)
1：10 to 1：40.
6. the method as described in claim 1, it is characterised in that the modification group includes amino group, carboxylic group etc.；Institute
Stating biomolecule includes any one in antibody, DNA fragmentation and bio-ligand.
7. method as claimed in any one of claims 1 to 6, it is characterised in that the described method comprises the following steps：
(1) preparation of small gold nano grain@copper sulfides:
The sodium citrate solution that 1mL concentration is 1% is added in the chlorauric acid solution for being 0.015mmol to the amount of 50mL materials,
Reaction obtains small gold nano grain after 20 minutes, and the CTAB that 10mL concentration is 0.5M is added into reaction solution, then will
0.008mmol thiobenzoate nickel and 0.003mmol copper chloride are added in small gold nano grain, then by this mixture
It is put into autoclave, carries out 135 degrees Celsius and react 2 hours；Small gold nano grain@copper sulfide particles progress centrifugation to preparation is washed
Wash, be dissolved in 20mL high purity waters；
(2) gold nano star vulcanizes the preparation of copper compound structure：
The HAuCl for being 0.02mmol to the amount of 50mL materials45 are stirred after middle addition 4mL small gold nano grain@copper sulfide particles
Minute, 0.0005mmol silver nitrate and 0.025mol ascorbic acid are then added, reaction carries out centrifugation standby after 1 minute
With；
(3) preparation of gold nano star@copper sulfide photo-thermal probes：
Cross-linking reaction is carried out using the amino group of composite structure surface or carboxyl group, so as to realize to biomolecule antibody
Link；Under 37 degree of environment, 0.05mmol antibody molecule is added in 0.005mmol composite construction, then under 37 degree
Carry out crosslinking 4 hours, then carry out washing centrifugation, finally under the effect of extraneous light field, realize to the fluorescence labeling of cancer cell and
Photo-thermal therapy.
8. nanometer star@copper sulfide photo-thermal probes prepared by claim 1-7 any one methods described.
9. as claimed in claim 8 nanometer of star@copper sulfides photo-thermal probe is oriented in cancer cell and followed the trail of, the photo-thermal therapy of cancer cell
In application.
10. application as claimed in claim 9, it is characterised in that the cancer cell includes all malignant cells.
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| CN107778411A (en) * | 2017-10-24 | 2018-03-09 | 东华大学 | A kind of preparation method of the gold nano star of surface modification Thermo-sensitive saccharide-based polymer |
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| CN114199816A (en) * | 2021-11-22 | 2022-03-18 | 湖北大学 | Near-infrared light excitation-based photo-thermal sensor for detecting biomarker, preparation method thereof and application thereof in marker detection |
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| SANTANA BALA LAKSHMANAN等: "Local Field Enhanced Au/CuS Nanocomposites as Efficient Photothermal Transducer Agents for Cancer Treatment", 《JOURNAL OF BIOMEDICAL NANOTECHNOLOGY》 * |
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| CN107778411A (en) * | 2017-10-24 | 2018-03-09 | 东华大学 | A kind of preparation method of the gold nano star of surface modification Thermo-sensitive saccharide-based polymer |
| CN112986561A (en) * | 2021-02-26 | 2021-06-18 | 福建师范大学 | Multimode immune instant analysis excited by nano titanium carbide hybrid |
| CN114199816A (en) * | 2021-11-22 | 2022-03-18 | 湖北大学 | Near-infrared light excitation-based photo-thermal sensor for detecting biomarker, preparation method thereof and application thereof in marker detection |
| CN114199816B (en) * | 2021-11-22 | 2023-11-03 | 湖北大学 | Photothermal sensor for detecting biological marker based on near infrared light excitation, preparation method thereof and application thereof in marker detection |
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Application publication date: 20170915 |