CN106680252B - A kind of fluorescent mark carrier and preparation method thereof based on nanotube - Google Patents
A kind of fluorescent mark carrier and preparation method thereof based on nanotube Download PDFInfo
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- CN106680252B CN106680252B CN201611055447.4A CN201611055447A CN106680252B CN 106680252 B CN106680252 B CN 106680252B CN 201611055447 A CN201611055447 A CN 201611055447A CN 106680252 B CN106680252 B CN 106680252B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a kind of fluorescent mark carrier and preparation method thereof based on nanotube.Fluorescent mark carrier of the invention includes: a nanometer inside pipe wall, quantum structure and nanometer pipe outer wall；The present invention carries out the size of accuracy controlling nano tube structure by control growth conditions according to the size for designing nano tube structure the characteristics of quasi- load；Fixed temperature annealing process guarantees that the nano wire in nucleocapsid structure decomposes completely, does not destroy the quantum structure being limited between nanometer inside pipe wall and nanometer pipe outer wall；The fluorescent-labeled portions of nanotube use semiconductor quantum structure, have fluorescence intensity high, and the duration is long, and spectrochemical property is stablized, and are not susceptible to photobleaching, high efficiency radiation recombination；And it is possible to be excited using continuous wide range, absorption coefficient is big, and fluorescence emission peak is narrow, no wavelength tail, can identification height；Nano tube structure can both realize the fluorescent marker delivery of the load in pipe, moreover it is possible to carry out traditional packaging type or the delivery of convolution fluorescent marker.
Description
Technical field
The present invention relates to the preparation method of fluorescent mark carrier more particularly to a kind of fluorescent mark carriers based on nanotube
Preparation method.
Background technique
Fluorescent labelling techniques originate from the 1940s, earliest for labelled antibody to detect corresponding antigen.With
The development in the fields such as the progress of science and technology and biomedicine, material science, the target of Cell-oriented scale or molecule, atomic scale
One of multiple subjects such as medicine, biology, chemistry and materialogy and the goal in research in field are had become to detection and targeted therapy,
The marking of drug, reagent etc., lossless delivery are accurate medical treatment, the critical problem that precisely detection etc. is achieved.Tradition is glimmering
Method used by signal be mainly using there is fluorescent characteristic or can generate after combining the chemical reagent of fluorescent characteristic into
Line flag, such as fluoresceins dyestuff, dye stuff of rhodamine kinds, cyanine dyes, green fluorescent protein.With the hair of semiconductor technology
Exhibition, the quantum dot with nano-grade size are gradually applied to fluorescent marker.Chan and Nie and Bruchez in 1998 etc. is for the first time
HeLa cell and 3T3 fibroblast is marked with quantum dot in success, indicates that quantum dot starts in the application of field of biology
Starting.But traditional Quantum Dot Labeling method is not avoided that damage, residual or diffusion of the labeled object in transport process,
Other non-detections or treatment object are caused to be affected, to bring interference to detection and analysis.Conventional tag object is different from (as measured
Sub- point) be wrapped in interior mode, a kind of labeled object is placed in the structure (such as nanotube) in marker, can effectively overcome on
Problem is stated, realizes targeting detection or treatment for target.The hollow structure of semiconducting nanotubes can be bioprotein, drug
Molecule or other inorganic material provide it is good transport carrier, meanwhile, the stable physics of semiconducting nanotubes and chemical property can
The lossless transport of carrying material to ensure, and high efficiency may be implemented by the coupling quantum spot in nanotube or Quantum Well
Fluorescent emission.The controllable preparation for having both the fluorescent mark carrier of label and transportation function, energy are realized using semiconducting nanotubes
Enough development for effectively pushing Related Research Domain.
Existing nanotube is mainly obtained by chemical synthesis process, the size (diameter, length and pipe thickness) of nanotube
It is difficult to accuracy controlling.Further, since the limitation of material and structure, existing nano-tube material exist do not shine, luminous efficiency is low or
The technical bottlenecks such as person's emission wavelength is non-adjustable.The above technological difficulties make for the preparation of the nanotube of specific wavelength and specific dimensions
It is difficult to realize.
Summary of the invention
For the above problems of the prior art, the invention proposes a kind of fluorescent mark carriers based on nanotube
And preparation method thereof, the fluorescent mark carrier based on nanotube can be prepared, the diameter to nanotube, tube wall, length are passed through
The controllable of the fluorescent mark carrier based on nanotube with high-efficiency fluorescence emission function is realized in adjusting with coupling quantum structure
Preparation.Using biology, chemically or physically method will be placed in nanotube to load, and the delivery to predetermined substance can be realized.
It is an object of the present invention to provide a kind of fluorescent mark carriers based on nanotube.
Fluorescent mark carrier based on nanotube of the invention includes: a nanometer inside pipe wall, quantum structure and nanometer pipe outer wall；
Wherein, the vertical growth nano wire in growth substrates；In the outside growing nano-tube inner wall of nano wire, nanometer inside pipe wall package is received
The side wall of rice noodles and top, in barrel-shaped；In the apical growth quantum structure of nanometer inside pipe wall；The luminescence band of quantum structure and inspection
It is consistent to survey wave band；In the side wall of nanometer inside pipe wall and the surface growing nano-tube outer wall of quantum structure, nanometer pipe outer wall package
The side wall and quantum structure thereon of nanometer inside pipe wall, in barrel-shaped；Outside nano wire, nanometer inside pipe wall, quantum structure and nanotube
Wall forms nucleocapsid structure；Nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates, and high temperature is carried out under fixed temperature
It makes annealing treatment, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer inside pipe wall, quantum structure and nanometer pipe outer wall
Nano tube structure；Quantum structure as fluorescent-labeled portions be located at barrel-shaped nanometer inside pipe wall and nanometer pipe outer wall top it
Between, three-dimensional quantum limitation is formed, realizes that efficient radiation recombination shines in the detection process.
The material of nano wire is the binary or ternary alloy of II-VI group or iii-v, the diameter of nano wire is 10~
100nm is highly 0.1~5 μm.
Nanometer pipe outer wall and nanometer inside pipe wall use identical material, and decomposition temperature is higher than the decomposition temperature of nano wire,
It is respective to collectively form nanotube walls with a thickness of 0.2~10nm, nanometer inside pipe wall and nanometer pipe outer wall.Decomposition temperature refers to material
In interatomic chemical bond start fracture when temperature.
Quantum structure between nanometer inside pipe wall and the top of nanometer pipe outer wall, is formed good as fluorescent-labeled portions
Three-dimensional quantum limitation so that not impacting in high-temperature annealing process to quantum structure, and quantum structure may be implemented
Alloy ordered arrangement can be realized efficient radiation recombination in the detection process and shine；The form of quantum structure is single quantum
Trap or multiple quantum wells, or be single quantum dot or multi layered quantum dots；The emission wavelength of quantum structure can within the scope of 200~2000nm
It adjusts.
The decomposition temperature that the fixed temperature of high annealing is greater than nano wire is less than the decomposition temperature of nanotube walls simultaneously, it is ensured that
Nano wire is completely broken down, and nanotube walls are not destroyed；The decomposition temperature of quantum structure and the fixed temperature of high annealing do not have
There is direct relation, quantum structure will not be destroyed in annealing process.
It is another object of the present invention to provide a kind of preparation methods of fluorescent mark carrier based on nanotube.
The preparation method of fluorescent mark carrier based on nanotube of the invention, comprising the following steps:
1) growth substrates are provided, growth substrates have the crystal face for being suitble to nano wire vertical growth；
2) according to the property of load, the parameter of nano tube structure is set, the parameter of nano tube structure includes nanotube knot
The internal diameter of structure, length, nanometer inside pipe wall and nanometer pipe outer wall thickness；
3) the vertical growth nano wire in growth substrates is received by the line ratio and growth time, control that control growth source
The diameter and height of rice noodles；
4) nanometer is controlled by controlling the line ratio and growth time in growth source in the external long nanotube inner wall of nano wire
The thickness of inside pipe wall, nanometer inside pipe wall wrap up side wall and the top of nano wire；
5) according to detection wave band, design emission wavelength and the detection consistent quantum structure of wave band, on the top of nanometer inside pipe wall
Hold grown quantum structure；
6) in the side wall of nanometer inside pipe wall and the surface growing nano-tube outer wall of quantum structure, pass through control growth source
Line ratio and growth time, control the thickness of nanometer pipe outer wall, and nanometer pipe outer wall wraps up the side wall and thereon of nanometer inside pipe wall
Quantum structure forms nucleocapsid structure；
7) nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates；
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer
The nano tube structure of inside pipe wall, nanometer pipe outer wall and quantum structure；
9) cleaning treatment is carried out to nano tube structure, obtains clean nano tube structure；
10) nano tube structure is dispersed in solution, using centrifugal process, extracts nano tube structure of uniform size；
11) load is placed in nano tube structure, realize based on nano tube structure can fluorescent marker to load
It transports.
Wherein, in step 1), the surface of growth substrates can be realized II-VI group or the binary or ternary of iii-v is closed
The vertical growth of golden material, the direction of growth of nano wire is along growth substrates normal to a surface direction.
In step 2), the features such as load size, composition form, the parameter of nano tube structure is designed, is wrapped
Include the thickness of the internal diameter of nano tube structure, length, nanometer inside pipe wall and nanometer pipe outer wall.
In step 3), the growth pattern of nano wire uses selective area growth, or uses self-organizing growth.Selective area growth is
Nano wire is grown in a part of growth substrates.Self-organizing growth is to start nano wire after self-organizing nucleation in growth substrates
Growth.The material of nano wire uses the binary or ternary alloy of II-VI group or iii-v.The mode of growth nano wire uses
Molecular beam epitaxy MBE, metal-organic chemical vapor deposition equipment MOCVD, chemical vapor deposition CVD or pulse laser deposition PLD etc..
According to the parameter designed in step 2), the line in II race and VI race or III group and V race growth source when growth time is selected,
To control the diameter (10~100nm) and height (0.1~5 μm) of nano wire.
In step 4), the decomposition temperature of nanotube inner-wall material is greater than the decomposition temperature of nano-material, using II-VI
The ternary or bianry alloy of race or iii-v select II race and VI race according to the thickness of the nanometer inside pipe wall designed in step 2)
Or the line when growth time of III group and V race growth source, to control the thickness (0.2~10nm) of nanometer inside pipe wall.
In step 5), according to used detection wave band, design quantum structure so that the emission wavelength of quantum structure with
It is consistent to detect wave band.The material and nano wire, nanometer inside pipe wall and nanometer pipe outer wall that quantum structure uses belong to same material body
System.The form of quantum structure is single quantum well or multiple quantum wells, or is single quantum dot or multi layered quantum dots.
In step 6), nanometer pipe outer wall and nanometer inside pipe wall use identical material, are received according to what is designed in step 2)
Mitron outer wall thickness, the line ratio of selection and identical growth source in step 4) control growth time, to control outside nanotube
The thickness (0.2~10nm) of wall, nano wire, nanometer inside pipe wall, quantum structure and nanometer pipe outer wall form nucleocapsid structure.
In step 7), nucleocapsid structure is removed from growth substrates, is dispersed in the surface at high temperature-resistant liner bottom.High temperature resistant
The surface of substrate needs cleaning, and nucleocapsid structure is avoided to be contaminated.The dispersing mode of nucleocapsid structure uses solwution method, i.e., first will
Nucleocapsid structure ultrasonic disperse is then transferred on high temperature-resistant liner bottom into solution；Or use physical method, i.e., directly by core-shell structure copolymer knot
Structure is dispersed directly on high temperature-resistant liner bottom by the methods of removing.
In step 8), the fixed temperature of annealing requires the decomposition temperature for being higher than nano wire, while being lower than nanometer inside pipe wall
With the decomposition temperature of nanometer pipe outer wall.Anneal environment, can according to material property using vacuum, air, nitrogen or inert gas etc.
To adjust.
In step 9), using the impurity introduced in hydrogen gas plasma removal annealing process, clean nanotube is obtained
Structure.
In step 10), solution is generally not acrid volatile liquid, such as alcohol, isopropanol.According to nanometer
The specific size (length and outer diameter) of pipe structure selects centrifugation rate, removes nano tube structure damaged in above-mentioned treatment process,
Obtain nano tube structure of uniform size.
In step 11), the method for load merging nano tube structure includes: solwution method, sedimentation, siphonage etc., tool
Body method need to be selected according to the characteristics of load, and load is placed in nano tube structure by final realize, without destroying load
And nano tube structure.
Advantages of the present invention:
(1) present invention is according to the size for designing nano tube structure the characteristics of intending load, diameter, length including nanotube
And pipe thickness, the size of accuracy controlling nano tube structure is carried out by control growth conditions；
(2) fixed temperature annealing process guarantees that the nano wire in nucleocapsid structure decomposes completely, does not destroy and be limited to receive
Quantum structure between mitron inner wall and nanometer pipe outer wall, meanwhile, it is capable to the alloy order in quantum structure is further increased,
Ensure the high efficiency radiation recombination of quantum structure；
(3) fluorescent-labeled portions of nanotube use semiconductor quantum structure, have fluorescence intensity high, and the duration is long,
Spectrochemical property is stablized, and photobleaching is not susceptible to；And absorption coefficient is big, and fluorescence emission peak is narrow, no wavelength tail, can identification
It is high；
(4) nano tube structure can both realize the fluorescent marker delivery of the load in pipe, moreover it is possible to carry out traditional packaging type
Or convolution fluorescent marker delivery.
Detailed description of the invention
Fig. 1 be the fluorescent mark carrier preparation method according to the present invention based on nanotube obtain in growth substrates
The schematic diagram of nucleocapsid structure；
Nucleocapsid structure is transferred to resistance to by Fig. 2 for the fluorescent mark carrier preparation method according to the present invention based on nanotube
Schematic diagram in high temperature substrate, wherein (a) is the schematic diagram before annealing, is (b) schematic diagram after annealing；
Fig. 3 is the fluorescent mark carrier that the fluorescent mark carrier preparation method according to the present invention based on nanotube obtains
Experimental results figure, wherein (a) is the scanning electron microscope diagram of the nucleocapsid structure before annealing, (b) at annealing
The scanning electron microscope diagram of obtained nano tube structure after reason (c) is the saturating of the nano tube structure obtained after making annealing treatment
Penetrate electron microscope picture.
Specific embodiment
With reference to the accompanying drawing, by embodiment, the present invention will be further described.
Embodiment
As shown in Figure 1, the fluorescent mark carrier based on nanotube of the present embodiment includes: nanometer inside pipe wall 31, Quantum Junction
Structure 4 and nanometer pipe outer wall 32, nanometer inside pipe wall 31 and nanometer pipe outer wall 32 collectively form nanotube walls 3；Wherein, in growth substrates
Vertical growth nano wire 2 on 1；Side wall and the top of nano wire 2 are wrapped up in the external long nanotube inner wall 31 of nano wire；In nanotube
The apical growth quantum structure 4 of inner wall 31；Outside the side wall of nanometer inside pipe wall 31 and the apical growth nanotube of quantum structure 4
Wall 32, nanometer pipe outer wall 32 wrap up the side wall of nanometer inside pipe wall 31 and the top of quantum structure 4, form nucleocapsid structure.
As shown in Fig. 2, nucleocapsid structure is transferred on high temperature-resistant liner bottom 6 from growth substrates 1, by the high temperature anneal, make
Nano wire 2 inside nucleocapsid structure decomposes, and obtains the nano tube structure 5 collectively formed by nanotube walls 3 and quantum structure 4.
In the present embodiment, AlN based nanotube structure is prepared, growth substrates use Si (111) face；The material of nanometer pipe outer wall
Using AlN, quantum well structure is single quantum well GaN, and the material of nanometer inside pipe wall uses AlN, and the material of nano wire uses GaN；
Nucleocapsid structure is grown on Si (111) face using molecular beam epitaxy MBE technology；Growth course carries out in ultrahigh vacuum chamber,
High-purity (7N) source metal is generated by the source K-Cell furnace；Nitrogen source uses radio frequency plasma nitrogen source.
The preparation method of the fluorescent mark carrier based on nanotube of the present embodiment, comprising the following steps:
1) growth substrates are provided, growth substrates 1 have the crystal face for being suitble to nano wire vertical growth:
The vertical growth of nano wire, nano wire edge may be implemented in GaN on Si (111) faceDirection growth, selects Si
(111) as the growth substrates of nano wire 1.
2) according to the property of load, the structural parameters of nanotube are set, internal diameter, length, inner wall including nanotube and
Outer wall thickness:
Intending load in the present embodiment is metal Al, the internal diameter that nanotube is arranged is 50nm, length 750nm, inner wall and
Outer wall thickness is 1nm.
3) the vertical growth nano wire in growth substrates is received by the line ratio and growth time, control that control growth source
The diameter and height of rice noodles:
Utilize the nanometer of molecular beam epitaxy MBE method upright GaN of self-assembled growth in the growth substrates 1 of Si (111)
Line 2, growth source used are the gallium source (Ga) and the source plasma nitrogen (N), and selecting the line ratio in the source Ga/N is 1/5, growth
Time is 100min, and it is highly 700nm that the diameter of nano wire, which is 50nm,.
4) nanometer is controlled by controlling the line ratio and growth time in growth source in the external long nanotube inner wall of nano wire
The thickness of inside pipe wall, nanometer inside pipe wall wrap up side wall and the top of nano wire:
The decomposition temperature of GaN is 850 DEG C under vacuum, and the decomposition temperature of AlN is 1040 DEG C, therefore, in the nano wire 2 of GaN
AlN nanometers of inside pipe walls 31 of outer wall and apical growth, growth source used be the metallic aluminium source (Al) and the source plasma nitrogen (N),
The line ratio for selecting the source Al/N is 1/20, and growth time 10min, AlN nanometer inside pipe wall 31 is with a thickness of 1nm.
5) according to detection wave band, design emission wavelength quantum structure consistent with detection wave band, on the top of nanometer inside pipe wall
Grown quantum structure:
For the detection wave band that the present embodiment uses for ultraviolet band (200-400nm), design quantum structure 4 is that GaN/AlN is mono-
Quantum Well, emission wavelength is in 280nm.
6) in the side wall of nanometer inside pipe wall and the surface growing nano-tube outer wall of quantum structure, pass through control growth source
Line ratio and growth time, control the thickness of nanometer pipe outer wall, and nanometer pipe outer wall wraps up the side wall and thereon of nanometer inside pipe wall
Quantum structure forms nucleocapsid structure:
In the nanometer pipe outer wall 32 of the surface growing AIN of the side wall and quantum structure 4 of the nanometer inside pipe wall 31 of AlN, institute
Growth source is the metallic aluminium source (Al) and the source plasma nitrogen (N), and selecting the line ratio in the source Al/N is 1/20, and growth time is
The nanometer pipe outer wall 32 of 10min, AlN are with a thickness of 1nm, GaN nano wire 2, the nanometer inside pipe wall 31 of AlN, quantum structure 4 and nanometer
Pipe outer wall 32 forms nucleocapsid structure.
7) nucleocapsid structure is removed from substrate 1, and is dispersed to 6 surface of high temperature-resistant liner bottom of clean Si (111), such as
Shown in Fig. 2 (a).
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including nanometer
The nano tube structure of inside pipe wall, nanometer pipe outer wall and quantum structure:
In vacuum environment, 900 DEG C (850 DEG C < 900 DEG C < 1040 DEG C) carry out annealing 30min, make in nucleocapsid structure
The nano wire 2 in portion decomposes, and obtaining on top includes the nano tube structure 5 of AlN/GaN/AlN single quantum well, such as Fig. 2 (b) institute
Show.Fig. 3 (a) and (b) are respectively sem test before nano tube structure 5 is annealed in the present embodiment and after annealing as a result, Fig. 3
It (c) is the transmissioning electric mirror test result of the nano tube structure 5 obtained after annealing.
9) nano tube structure is handled using hydrogen gas plasma, obtains clean nano tube structure:
Using the hydrogen gas plasma of 1.2sccm/400W, surface cleaning is carried out to nano tube structure 5 and handles 5min, removal
Impurity present in nano tube structure 5 etc. in annealing process.
10) nano tube structure is dispersed in solution, using centrifugal process, extracts the nano tube structure with uniform-dimension:
Will by step 5), treated that nano tube structure 5 is dispersed in aqueous isopropanol, handled using centrifuge,
Damaged nano tube structure during removal annealing and cleaning treatment, it is final obtain diameter be 50nm, length 750nm, tube wall
With a thickness of the nano tube structure 5 of 2nm, luminescence generated by light test confirms top AlN/GaN/AlN single quantum well fluorescent marker structure
Emission wavelength is 280nm, to prepare fluorescent mark carrier.
11) by load be placed in nano tube structure in, can be realized based on nano tube structure can fluorescence mark to load
Note transports:
The nano tube structure 5 obtained in step 6) is dispersed on Si (111) substrate, molecular beam epitaxy MBE technology is utilized
Al metal, is then injected into the inside of nano tube structure 5 by deposited metal Al drop using siphonic effect；It will be marked with metal later
The nano tube structure 5 of Al is dispersed in aqueous isopropanol again, using the laser excitation of 266nm, finds shining for 280nm, and
Determine its position.The fluorescent marker delivery to metal Al is realized using nano tube structure 5.
It is finally noted that the purpose for publicizing and implementing mode is to help to further understand the present invention, but ability
The technical staff in domain is understood that without departing from the spirit and scope of the invention and the appended claims, various replacements and
Modification is all possible.Therefore, the present invention should not be limited to embodiment disclosure of that, the scope of protection of present invention with
Subject to the range that claims define.
Claims (10)
1. a kind of preparation method of the fluorescent mark carrier based on nanotube, which is characterized in that the preparation method includes following
Step:
1) growth substrates are provided, growth substrates have the crystal face for being suitble to nano wire vertical growth；
2) according to the property of load, the parameter of nano tube structure is set, the parameter of nano tube structure includes nano tube structure
Internal diameter, length, nanometer inside pipe wall and nanometer pipe outer wall thickness；
3) the vertical growth nano wire in growth substrates controls nano wire by controlling the line ratio and growth time in growth source
Diameter and height；
4) it is controlled in nanotube in the external long nanotube inner wall of nano wire by controlling the line ratio and growth time in growth source
The thickness of wall, nanometer inside pipe wall wrap up side wall and the top of nano wire；
5) raw on the top of nanometer inside pipe wall according to detection wave band, design emission wavelength and the detection consistent quantum structure of wave band
Long quantum structure；
6) in the side wall of nanometer inside pipe wall and the surface growing nano-tube outer wall of quantum structure, by the line for controlling growth source
Than and growth time, control the thickness of nanometer pipe outer wall, nanometer pipe outer wall wraps up the side wall and quantum thereon of nanometer inside pipe wall
Structure forms nucleocapsid structure；
7) nucleocapsid structure is transferred on high temperature-resistant liner bottom from growth substrates；
8) the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure decomposes, and obtains including in nanotube
The nano tube structure of wall, nanometer pipe outer wall and quantum structure；
9) cleaning treatment is carried out to nano tube structure, obtains clean nano tube structure；
10) nano tube structure is dispersed in solution, using centrifugal process, extracts nano tube structure of uniform size；
11) load is placed in nano tube structure, realizes transporting to load fluorescent marker based on nano tube structure.
2. preparation method as described in claim 1, which is characterized in that in step 3), the growth pattern of nano wire is using choosing
Area's growth, or use self-organizing growth.
3. preparation method as described in claim 1, which is characterized in that in step 5), according to used detection wave band, if
Minor structure is measured, so that the emission wavelength of quantum structure is consistent with detection wave band；Material and nano wire that quantum structure uses are received
Mitron inner wall and nanometer pipe outer wall belong to same material system；The form of quantum structure be single quantum well or multiple quantum wells, or
For single quantum dot or multi layered quantum dots.
4. preparation method as described in claim 1, which is characterized in that in step 7), by nucleocapsid structure from growth substrates
It removes, is dispersed in the surface at high temperature-resistant liner bottom；The dispersing mode of nucleocapsid structure uses solwution method, i.e., first by nucleocapsid structure ultrasound
It is dispersed in solution and is then transferred on high temperature-resistant liner bottom；Or use physical method, i.e., nucleocapsid structure is directly passed through into the side of removing
Method is dispersed directly on high temperature-resistant liner bottom.
5. preparation method as described in claim 1, which is characterized in that in step 8), the fixed temperature of annealing requires to be higher than
The decomposition temperature of nano wire, while being lower than the decomposition temperature of nanometer inside pipe wall and nanometer pipe outer wall；Anneal environment uses vacuum, sky
Gas, nitrogen or inert gas.
6. preparation method as described in claim 1, which is characterized in that in step 10), solution is easily waved to be not acrid
Lotion body；According to the specific size of nano tube structure, centrifugation rate is selected, removes damaged nano tube structure, it is equal to obtain size
Even nano tube structure.
7. a kind of fluorescent mark carrier based on nanotube, which is characterized in that the fluorescent mark carrier includes: in nanotube
Wall, quantum structure and nanometer pipe outer wall；Wherein, the vertical growth nano wire in growth substrates；In the outside of nano wire, growth is received
Mitron inner wall, the side wall of the nanometer inside pipe wall package nano wire and top, in barrel-shaped；In the apical growth amount of nanometer inside pipe wall
Minor structure；The luminescence band of the quantum structure is consistent with detection wave band；In the side wall and quantum structure of nanometer inside pipe wall
Surface growing nano-tube outer wall, the side wall of nanometer pipe outer wall package nanometer inside pipe wall and quantum structure thereon, in barrel-shaped；
The nano wire, nanometer inside pipe wall, quantum structure and nanometer pipe outer wall form nucleocapsid structure；The nucleocapsid structure is served as a contrast from growth
It is transferred on bottom on high temperature-resistant liner bottom, the high temperature anneal is carried out under fixed temperature, the nano wire inside nucleocapsid structure point
Solution, obtain include nanometer inside pipe wall, quantum structure and nanometer pipe outer wall nano tube structure.
8. fluorescent mark carrier as claimed in claim 7, which is characterized in that the nanometer pipe outer wall and nanometer inside pipe wall use
Identical material, decomposition temperature are higher than the decomposition temperature of nano wire.
9. fluorescent mark carrier as claimed in claim 7, which is characterized in that the form of the quantum structure be single quantum well or
Multiple quantum wells, or be single quantum dot or multi layered quantum dots；The emission wavelength of the quantum structure can within the scope of 200~2000nm
It adjusts.
10. fluorescent mark carrier as claimed in claim 7, which is characterized in that the material of the nano wire be II-VI group or
The diameter of the binary or ternary alloy of iii-v, the nano wire is 10~100nm, is highly 0.1~5 μm.
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| CN1884430B (en) * | 2006-06-30 | 2010-07-28 | 上海师范大学 | Fluorescent carbon nanometer tube and its preparation method and application |
| TWI340730B (en) * | 2007-05-30 | 2011-04-21 | Nat Univ Tsing Hua | A visualization method of carbon nanotubes |
| CN101974326B (en) * | 2010-09-21 | 2013-06-19 | 上海大学 | Method for preparing novel fluorescent silica nanospheres |
| CN102416180B (en) * | 2011-12-14 | 2013-04-17 | 浙江理工大学 | Functional integrated medicament carrier and preparation method thereof |
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