CN106335885A - Black phosphorus nanosheet and preparation method and application thereof - Google Patents
Black phosphorus nanosheet and preparation method and application thereof Download PDFInfo
- Publication number
- CN106335885A CN106335885A CN201610680032.XA CN201610680032A CN106335885A CN 106335885 A CN106335885 A CN 106335885A CN 201610680032 A CN201610680032 A CN 201610680032A CN 106335885 A CN106335885 A CN 106335885A
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- nanometer sheet
- preparation
- dispersion liquid
- ultrasonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention provides black phosphorus nanosheet and a preparation method and application thereof. The method comprises the following steps: placing black phosphorus powder into anaerobic water to form a dispersion of black phosphorus powder, and selectively controlling pH of the dispersion to alkaline level; carrying out ultrasonic treatment on the dispersion of black phosphorus powder in an inert environment; and after the ultrasonic treatment, centrifuging and collecting a supernatant so as to obtain the black phosphorus nanosheet. The invention also provides the black phosphorus nanosheet prepared by the method and application of the black phosphorus nanosheet. As no organic solvent is used by the method, the prepared black phosphorus nanosheet has no organic solvent residue, will not pollute the environment and can be applied in the field of biomedicine.
Description
Technical field
The present invention relates to a kind of black phosphorus nanometer sheet and preparation method and application, belong to novel black phosphorus nano material field.
Background technology
Two-dimensional layer material, such as Graphene and transient metal sulfide (tmds) etc., due to their excellent specific properties, become
The nano material of bright prospects is had for a class in basic research and potential application.Black phosphorus, is a kind of most stable of homoatomic of phosphorus
Obform body, it has similar but different from graphene sheet layer assembling structure waveform layer structure, this unique waveform stratiform knot
Structure imparts the many unique physicochemical properties of black phosphorus, and such as black phosphorus possesses the unexistent semiconductor direct bandgap of Graphene, has super
Go out the electron mobility～1,000cm of transient metal sulfide two-dimensional material2v-1s-1, spectrum includes whole visible ray to closely red
Exterior domain, therefore, black phosphorus has broad application prospects in fields such as photoelectric device, sensor, solar cells.Especially,
Two-dimentional black phosphorus nanometer sheet, because of itself optical property and nanometer size effect, shows in terms of photo-thermal and photodynamic therapy
Splendid function, simultaneously as phosphorus be biological necessary in vivo element so as to biomedical sector application have no comparable
The advantage intended, therefore black phosphorus has huge using value in biomedical sector.
In the preparation method of current black phosphorus, mechanical stripping method is to prepare a kind of mode of black phosphorus nanometer sheet, is also
Currently main preparation method, such as document (nat.nanotechnol.2014,9,372), this adhesive tape is peeled off by hand repeatedly
Method, the black phosphorus nanometer sheet of the several nano thickness that can prepare, but Product size is larger, yield is extremely low, so only fitting
Basic research for electronics and photoelectric device is it is impossible to meet the demand of application study.And the application for some key areas,
As biomedicine, ultra-fast optical, battery electrode, electronic printing and solar cell etc., need to prepare substantial amounts of black phosphorus nanometer sheet.
In order to meet needs, the method that have recently emerged some liquid phase peels off block black phosphorus in organic solution, such as document
(angew.chem.int.ed.2015,54,1–6；adv.mater.2015,27,1887；chem.commun.2014,50,
13338.) refer to: in the organic solvents such as nmp, dmf, dmso, chp, black phosphorus can be prepared in a large number with the method for water bath sonicator and receive
The dispersion liquid of rice piece, then black phosphorus nanometer sheet is obtained by centrifugation.When being prepared black phosphorus on a large scale in this way, a side
Face, due to relatively costly, easily causes environmental pollution, on the other hand because these organic solvents are difficult to remove, easily remains in black
The surface of phosphorus nanometer sheet, inevitably limits the application of black phosphorus nanometer sheet, especially in the application of biomedical sector.Cause
This, be badly in need of developing that a kind of low cost, environmental pollution be little, the preparation method of organic solvent-free residual black phosphorus nanometer sheet.
Content of the invention
Present invention is primarily targeted at providing a kind of preparation method of black phosphorus nanometer sheet, residual to organic solvent-free is obtained
The black phosphorus nanometer sheet stayed.
For this reason, on the one hand, the present invention provides a kind of preparation method of black phosphorus nanometer sheet, and wherein, methods described includes as follows
Step:
(1) black phosphorus powder is placed in formation black phosphorus powder dispersion liquid in anaerobic water；
Optionally, the ph making this dispersion liquid is alkalescence；Preferably, black phosphorus powder is placed in the alkaline anaerobic aqueous solution,
So that the ph of described black phosphorus powder dispersion liquid is alkalescence；
(2) in an inert atmosphere, ultrasonic described black phosphorus powder dispersion liquid, preferably ultrasonic power are water bath sonicator or probe is super
Sound；
(3) ultrasonic finish after, supernatant is collected by centrifugation, obtains described black phosphorus nanometer sheet.
Due to not using any organic solvent in the inventive method, therefore, the black phosphorus nanometer sheet being obtained by it is no organic molten
Agent remains, free from environmental pollution, can be applicable to biomedical sector.
In certain embodiments of the present invention it is preferable that step (1) is that black phosphorus powder is placed in the alkaline anaerobic aqueous solution
In, so that the ph of described black phosphorus powder dispersion liquid is alkalescence.Experiments show that in the case of other conditions identical,
The yield of black phosphorus nanometer sheet can be improved using the alkaline anaerobic aqueous solution compared with anaerobic water.
In certain embodiments of the present invention it is preferable that step (2) adopts black phosphorus powder dispersion described in Probe Ultrasonic Searching
Liquid.Experiments show that in the case of other conditions identical, being remarkably improved compared with water bath sonicator using Probe Ultrasonic Searching
The yield of black phosphorus nanometer sheet.
In certain embodiments of the present invention it is preferable that method of the present invention comprises the steps:
(1) black phosphorus powder is placed in the alkaline anaerobic aqueous solution, so that the ph of described black phosphorus powder dispersion liquid is alkalescence；
(2) in an inert atmosphere, black phosphorus powder dispersion liquid described in Probe Ultrasonic Searching；
(3) ultrasonic finish after, supernatant is collected by centrifugation, obtains described black phosphorus nanometer sheet.
As described above, the method that black phosphorus nanometer sheet is prepared in existing machinery stripping needs manpower manual operations, operating process is complicated,
It is difficult to repeat, yield is extremely low it is difficult to a large amount of prepare.Existing thin layer black phosphorus nanometer sheet liquid phase stripping method is all to be had using high boiling
Machine solvent (as nmp, dmf, dmso, chp etc.), when being prepared on a large scale, relatively costly, easily cause environmental pollution, and
It is difficult to remove completely from material surface, there is certain bio-safety hidden danger.And the method for the present invention does not use organic solvent, institute
The media security using is nontoxic, and process is simple is easy to operate, and manpower, cost of material are low, favorable reproducibility, economical and practical, it is possible to achieve
The low cost of black phosphorus nanometer sheet is " green " on a large scale to be produced, and does not produce secondary pollution problem to environment.By the inventive method institute
Prepared black phosphorus nanometer sheet not residual organic solvent, and obtained black phosphorus nanometer chip size is little, good dispersion.
The black phosphorus nanometer sheet of the present invention prepares in the anaerobic aqueous solution.The removing of anaerobic water oxygen, permissible
Effectively prevent the oxidation of black phosphorus nanometer sheet, improve its stability.Anaerobic water can commercially available or pass through this area conventional technique system
For obtaining, for example, a certain amount of ultra-pure water is placed in high-pressure sterilizing pot, obtains the ultra-pure water seething with excitement in the case of HTHP, so
Afterwards with controlling the nitrogen n of certain pressure intensity2Being passed through a period of time in water, thus removing the oxygen in ultra-pure water, obtaining ultrapure anaerobic
Water, then sealing is deposited, for using.
In certain embodiments of the present invention, water bath sonicator described in step (2) is with 100～500w (such as 300w)
Power ultrasonic 1～6h；Preferably, water bath sonicator is carried out using ultrasonic cleaning machine；
Probe Ultrasonic Searching described in step (2) be stop 1～10 second (for example work 2 seconds and stop 4 seconds) to work 1～10 second in the way of
Circulation is carried out, working time totally 1～6h, and power during work is 400～2000w；Preferably, institute is carried out using cell crushing instrument
State Probe Ultrasonic Searching.Circulated in the way of working 2 seconds and stopping 4 seconds for example with cell crushing instrument Probe Ultrasonic Searching and carry out, work 1～6h,
Power during work is 1200w.
Power during above-mentioned work is, for example, 400w, 800w, 1200w, 1600w, preferably 1200w.Above-mentioned working time example
As for 1h, 2h, 3h, 6h, preferably 3h.
Probe Ultrasonic Searching is more preferable than water bath sonicator peeling effect in same time.
In certain embodiments of the present invention, the ph controlling described black phosphorus powder dispersion liquid in step (1) is 9～12；
Preferably ph is 11.
It is highly preferred that step (1) is that black phosphorus powder is placed in formation black phosphorus in the alkaline anaerobic aqueous solution that ph is 11～12
Powder dispersion liquid；Preferably, this alkaline anaerobic aqueous solution is the Sodium Hydroxide Alkaline anaerobic aqueous solution.
The Sodium Hydroxide Alkaline anaerobic aqueous solution is with low cost, ratio organic solution safety economy, and ratio prepares yield in the aqueous solution
High.
In certain embodiments of the present invention, black phosphorus powder described in step (1) is to grind by black phosphorus bulk to obtain
's；Preferably, the particle diameter of described black phosphorus powder is 10～1000 μm.
In certain embodiments of the present invention, in described black phosphorus powder dispersion liquid, the concentration of black phosphorus is 0.5～5mg/ml.
Preferably 2mg/ml.
In certain embodiments of the present invention, the inert environments in step (2) are using inert gas and/or nitrogen shape
Become, described inert gas is, for example, argon gas.Inert gas and/or nitrogen can with starvation prevent from generating in preparation process black
Phosphorus nanometer sheet is oxidized.
In certain embodiments of the present invention, step (2), in ultrasonic procedure, controls described black phosphorus powder dispersion liquid
Temperature is 0～30 DEG C；Preferably employ ice bath and control temperature.Under condition of ice bath, heat production and radiating can be made to maintain one more
Stable level, can continuously high-power ultrasonic concussion.
In certain embodiments of the present invention, under the conditions of the rotating speed of centrifugation described in step (3) is 1000～5000rpm
(for example it is centrifuged 20min) after centrifugation 10～60min and take supernatant dispersion liquid.Preferably, rotating speed is 2000rpm, can under this rotating speed
Ensure that the quality (thin and thick of black phosphorus nanometer sheet and small size) of black phosphorus nanometer sheet also can take into account final products yield.
According to actual needs, aforementioned techniques means of the present invention can be mutually combined, such as in some embodiment party of the present invention
In formula, the preparation method of the present invention includes:
(1) with block black phosphorus as raw material, after ground one-tenth powder, anaerobic water or ph 9 are placed in the concentration of 0.5～5mg/ml
In the middle of～12 alkaline anaerobic aqueous solution；
(2) under the protection of inert gas, in the environment of ice bath temperature control, surpassed by the ultrasonic cleaning machine water-bath of 300w
Sound, or power is 400～2000w and the cell crushing instrument Probe Ultrasonic Searching of certain operation range, and intense sonic concussion 1～6 is little
When, then after 1000～5000rpm centrifugation 20min, take supernatant dispersion liquid, prepare thin layer black phosphorus nanometer sheet.
On the other hand, the present invention provides the black phosphorus nanometer sheet that prepared by said method it is preferable that this black phosphorus nanometer sheet
Thickness be 1～20nm, lateral dimension be 20～500nm.
The present invention preparation-obtained black phosphorus nanometer sheet do not contain residual organic solvent, biological safety is high, size is little, point
Scattered property is good, and tests and prove that the black phosphorus nanometer sheet that obtained of the present invention has good photo-thermal therapy ability, for biomedicine
Application lays the foundation.
Another further aspect, the present invention also provides above-mentioned black phosphorus nanometer sheet answering in the photo-thermal therapy agent of preparation treating cancer
With；Preferentially, described black phosphorus nanometer sheet is configured to solution, treating cancer under laser irradiates, it is highly preferred that by black phosphorus nanometer
Piece is configured to the solution that concentration is more than 150 μ g/ml, is 1w/cm in laser intensity2Under the conditions for the treatment of cancer.
Compared with prior art, the present invention has following Advantageous Effects:
1) solvent that the method for the present invention is adopted is the anaerobic water of safety non-toxic or the alkaline anaerobic aqueous solution, it is to avoid have
The presence of machine solvent.
2) aqueous solution that the method for the present invention adopts is anaerobic water, and the removing of anaerobic water oxygen can effectively prevent black
The oxidation of phosphorus nanometer sheet, improves its stability.
3) solvent that the method for the present invention is adopted is cheap, and cost of material is lower, economical convenient.
4) the Probe Ultrasonic Searching method that the method for the present invention can be adopted, method is simple to operation, saves manpower.
5) method of the present invention high yield can prepare that size is little, the black phosphorus nanometer sheet of good dispersion.
6) solvent safety that the method for the present invention is adopted is nontoxic, and process is simple is easy to operate, and manpower, cost of material are low, weight
Existing property is good, economical and practical, it is possible to achieve the low cost of black phosphorus nanometer sheet is " green " on a large scale to be produced, and environment is not produced secondary
Pollution problem.
7) the black phosphorus nanometer sheet being prepared by the method for the present invention has splendid photothermal deformation performance, has excellent
Photo-thermal killing tumor cell function, is a kind of outstanding photo-thermal therapy reagent.
Brief description
Fig. 1 is the absorption spectrum of the black phosphorus nanometer sheet that the embodiment of the present invention 1 is obtained；
Fig. 2 is the absorption spectrum of the black phosphorus nanometer sheet that the embodiment of the present invention 2 is obtained；
Fig. 3 is the absorption spectrum of the black phosphorus nanometer sheet that the embodiment of the present invention 3 is obtained；
Fig. 4 is the absorption spectrum of the black phosphorus nanometer sheet that the embodiment of the present invention 1～3 is obtained；
Fig. 5 is the concentration gradient absorption spectrum of black phosphorus nanometer sheet and calibration curve that the embodiment of the present invention 3 is obtained；
Fig. 6 is the transmission electron microscope picture (tem) of the black phosphorus nanometer sheet that the embodiment of the present invention 3 is obtained；
Fig. 7 is the photo-thermal heating curve of the black phosphorus nanometer sheet that the embodiment of the present invention 3 is obtained；
Fig. 8 is the cell photo-thermal therapy figure of the black phosphorus nanometer sheet that the embodiment of the present invention 3 is obtained；
Fig. 9 is cells survival rate after the photo-thermal therapy of black phosphorus nanometer sheet that the embodiment of the present invention 3 is obtained.
Specific embodiment
Described below is the preferred embodiment of the embodiment of the present invention it is noted that common skill for the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, some improvements and modifications can also be made, these improvement
It is also considered as the protection domain of the embodiment of the present invention with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to
Under specific embodiment, can be suitable carrying out change implement.
Anaerobic water in following examples is prepared as follows: a certain amount of ultra-pure water is placed in high-pressure sterilizing pot,
The ultra-pure water seething with excitement is obtained, then with controlling the nitrogen n of certain pressure intensity in the case of HTHP2It is passed through a period of time in water, from
And remove the oxygen in ultra-pure water, obtain ultrapure anaerobic water, then sealing is deposited, for using.
Embodiment 1
The present embodiment provides a kind of alkaline aqueous solution strip preparation method of two dimension black phosphorus nanometer sheet, and it includes walking as follows
Rapid:
Weigh 25mg gram of black phosphorus block in the glove box of applying argon gas, pulverize in mortar last, with 1mg/ml
Concentration be placed in pure anaerobic water.In n2Under the protection of gas, in the environment of ice bath temperature control, it is sealed in 50ml plastic tube,
By the ultrasonic cleaning machine water bath sonicator of 300w, sound wave shock 3 hours, then take with after the rotating speed centrifugation 20min of 2000rpm
Sorting dispersion liquid, prepares black phosphorus nanometer sheet dispersion liquid.
By the black phosphorus obtaining nanometer sheet dispersion liquid after 3 times of dilutions of anaerobic water, move in quartz glass ware, be placed in uv
In vis nir spectrophotometer, detect absorption curve, observe absorption spectrum, result is as shown in figure 1, find that gained absorption value is inclined
Little, black phosphorus nanometer sheet yield is relatively low.
Embodiment 2
The present embodiment provides a kind of alkaline aqueous solution strip preparation method of two dimension black phosphorus nanometer sheet, and it includes walking as follows
Rapid:
Weigh 25mg gram of black phosphorus block in the glove box of applying argon gas, pulverize in mortar last, with 1mg/ml
Concentration be placed in the middle of the pure anaerobic aqueous solution.In n2Under the protection of gas, in the environment of ice bath temperature control, it is sealed in 50ml plastics
Guan Zhong, by power be 1200w and operation range is the cell crushing instrument Probe Ultrasonic Searching that work 2s stops 4s, intense sonic concussion 3
Hour, then take supernatant dispersion liquid with after the rotating speed centrifugation 20min of 2000rpm, prepare black phosphorus nanometer sheet dispersion liquid.
By the black phosphorus obtaining nanometer sheet dispersion liquid after 3 times of dilutions of anaerobic water, move in quartz glass ware, be placed in uv
In vis nir spectrophotometer, detect absorption curve, observe absorption spectrum, result is as shown in Fig. 2 absorption curve is compared with embodiment 1
Rise it was demonstrated that in same solvent, same time, the black phosphorus nanometer sheet yield obtained by cell crushing instrument Probe Ultrasonic Searching is higher.
Embodiment 3
The present embodiment provides a kind of alkaline aqueous solution strip preparation method of two dimension black phosphorus nanometer sheet, and it includes walking as follows
Rapid:
Weigh 25mg gram of black phosphorus block in the glove box of applying argon gas, pulverize in mortar last, with 1mg/ml
Concentration be placed in ph 11 naoh alkalescence the anaerobic aqueous solution in the middle of.In n2Under the protection of gas, in the environment of ice bath temperature control,
It is sealed in 50ml plastic tube, by power be 1200w and operation range is that the clasmatosis instrument probe that work stops 4 seconds for 2 seconds surpasses
Sound, intense sonic shakes 3 hours, then takes supernatant dispersion liquid with after the rotating speed centrifugation 20min of 2000rpm, prepares black phosphorus
Nanometer sheet dispersion liquid.
By the black phosphorus obtaining nanometer sheet dispersion liquid after 3 times of dilutions of anaerobic water, move in quartz glass ware, be placed in uv
In vis nir spectrophotometer, detect absorption curve, observe absorption spectrum, result is as shown in figure 3, absorption curve is compared with embodiment
1st, 2 all have rising it was demonstrated that in same time, the naoh alkalescence cell crushing instrument as solvent for the anaerobic aqueous solution being 11 with ph value
Probe Ultrasonic Searching method, obtained black phosphorus nanometer sheet yield highest.
The absorption curve of embodiment 1～3 is put together and compares, as shown in figure 4, it can clearly be seen that in other condition phases
In the case of same, in embodiment 3, with the naoh alkalescence anaerobic aqueous solution of ph 11 as solvent, using cell crushing instrument Probe Ultrasonic Searching
Method, obtained black phosphorus nanometer sheet solution absorbs maximum, yield highest.
The black phosphorus nanometer sheet solution of preparation in embodiment 3 is configured to the solution of variable concentrations with 2 times of ratio gradient dilutions,
Absorption spectrum is tested and analyzed by uv vis nir spectrophotometer, result is as shown in figure 5, according to absorption intensity at 500nm, make
Make calibration curve, its r value has reached 0.999 it was demonstrated that absorption intensity is in good linear pass with the concentration of black phosphorus nanometer sheet solution
System, has confirmed obtained black phosphorus nanometer sheet yield highest in embodiment illustrated in fig. 43.
By the black phosphorus nanometer sheet solution of preparation in embodiment 3, drop on the micro-grid copper mesh with filter paper as bottom, be placed under normal temperature
Dry in the shade, after being repeated several times by, be placed in and overnight dry in the shade under normal temperature.It is subsequently placed in the knot observing black phosphorus nanometer sheet under transmission electron microscope
Structure and pattern.As shown in fig. 6, thin layer black phosphorus nanometer sheet thickness 1～20nm of obtaining, lateral dimension is about 500nm to result, dispersion
Property is good.
Embodiment 4
The photo-thermal heating curve of the black phosphorus nanometer sheet solution of preparation in detection embodiment 3, by the black phosphorus of preparation in embodiment 3
Nanometer sheet solution, be configured to respectively concentration be 50, the aqueous solution of 100,150,300 μ g/ml, 1ml is prepared each concentration of obtaining
Black phosphorus nanometer sheet solution be placed in transparent plastic ep pipe, with launch wavelength be 808nm, power be 1w/cm2Laser illumination
10min, measures solution temperature every 30s with visual infrared temperature imager, as a control group with pure water, draws photo-thermal liter simultaneously
Warm curve.Result is as shown in fig. 7, after laser irradiation 10min, black phosphorus nanometer sheet solution temperature gradually rises, and is in concentration dependant,
The black phosphorus nanometer sheet solution highest of 300 μ g/ml rises to 59.7 DEG C by 19.1 DEG C, and the ultrapure coolant-temperature gage as comparison does not have substantially
Become, this shows that the nanoscale black phosphorus that the present invention is obtained has outstanding photothermal deformation ability, is a kind of excellent optothermal material,
Photo-thermal therapy field has broad prospect of application.
Embodiment 5
The photo-thermal therapy effect of the black phosphorus nanometer sheet solution of preparation in detection embodiment 3, Apoptosis detection adopts
Calcein-am/pi living cells/dead cell double-staining.
Specifically comprise the following steps that and with trypsase (1:250), the c6 cell in logarithmic growth digested from blake bottle,
Make cell suspension, adjustment cell density is 5 × 104cells/ml.In 12 orifice plates, every hole adds cell suspension 1ml, Yu Han
There is the co of 5% volume fraction2In incubator, 37 DEG C of quiescent culture.When cell monolayer is paved with 12 orifice bore bottom, be separately added into through
Anaerobic water be diluted to concentration be 75 μ g/ml, the black phosphorus nanometer sheet solution of 150 μ g/ml, each concentration arrange 3 holes, arrange simultaneously with
Pbs is blank.Quiescent culture 4h in incubator.Suck the culture medium containing medicine, every hole is carefully added into 1ml pbs punching
Wash two to three times, suck pbs, every hole adds 1ml fresh culture, 12 orifice plates is placed under 808nm laser, uses 0.5w/ respectively
cm2、1w/cm2Irradiate 10min.
(calcein-am and pi is dense to prepare working solution according to the double staining kit of calcein-am/pi living cells/dead cell
Degree is respectively 2 μm and 4.5 μm), suck culture medium, every hole is each to add 500 μ l calcein-am and pi working solution, mixes, in 37
DEG C incubation 15min, is placed under inverted fluorescence microscope observation coloration result.Result is as shown in figure 8, be 0.5w/ in laser intensity
cm2When, the black phosphorus nanometer sheet solution than 75 μ g/ml for the 150 μ g/ml has stronger killing to tumour cell, but fails to kill completely,
Still there are a large amount of green cells (living cells)；Rise to 1w/cm with laser intensity2When, lethality is remarkably reinforced, and 150 μ g/ml's is black
In the hole of phosphorus nanometer sheet solution, cell is entirely killed, all becomes red cell (dead cell), presents powerful light
Heat cure ability.
Embodiment 6
In detection embodiment 3, the photo-thermal therapy effect of the black phosphorus nanometer sheet solution of preparation, detects cells survival using mtt method
Rate, specifically comprises the following steps that and is digested the c6 cell in logarithmic growth from blake bottle with trypsase (1:250), make
Cell suspension, adjustment cell density is 5 × 104cells/ml.In 96 orifice plates, every hole adds cell suspension 100 μ l, edge hole
With the pbs filling of same volume, in the co containing 5% volume fraction2In incubator, 37 DEG C of quiescent culture.Treat that cell monolayer is paved with
During 96 orifice bore bottom, be separately added into through anaerobic water be diluted to concentration be 75 μ g/ml, the black phosphorus nanometer sheet solution of 150 μ g/ml, often
Individual concentration arrange 6 parallel, five groups of same volume pbs negative controls are set simultaneously.Quiescent culture 4h in incubator.Suck and contain
There is the culture medium of medicine, every hole is carefully added into 100 μ l pbs and rinses two to three times, sucks pbs, every hole adds the fresh training of 150 μ l
Foster base, 96 orifice plates is placed under 808nm laser, uses 0.5w/cm respectively2、1w/cm2Irradiate 10min.Examine under a microscope cell
Apoptosis situation, adds the prewired mtt solution of 20 μ l in each hole, continue culture 4h, terminate culture, carefully suck the culture of in the hole
Base, each hole adds dimethyl sulfoxide (DMSO) 150 μ l, and being placed on low speed shaking table slow concussion 10min makes crystallization all dissolve, in full work(
Light absorption value at 490nm for each hole can be measured in ELIASA, draw cells survival rate figure.Result is as shown in figure 9, in laser intensity
For 0.5w/cm2When, the black phosphorus nanometer sheet solution than 75 μ g/ml for the 150 μ g/ml has stronger killing to tumour cell, but has failed
Entirely kill, cells survival rate is 51.43%, rises to 1w/cm with laser intensity2When, lethality is remarkably reinforced, 150 μ g/ml's
In the hole of black phosphorus nanometer sheet solution, cell is entirely killed substantially, and cells survival rate is only 6.63%, with embodiment 5 result phase
With, again demonstrate the powerful photo-thermal therapy ability of the black phosphorus nanometer sheet that the present invention is obtained, and its huge in biomedical sector
Big application potential.
Finally illustrate: above example is merely to illustrate implementation process and the feature of the present invention, and unrestricted is sent out
Bright technical scheme, although being described in detail to the present invention with reference to above-described embodiment, those of ordinary skill in the art should
Working as understanding: still the present invention can be modified or equivalent, without departing from the spirit and scope of the present invention any
Modification or local are replaced, and all should cover in the middle of protection scope of the present invention.
Claims (10)
1. a kind of preparation method of black phosphorus nanometer sheet, wherein, methods described comprises the steps:
(1) black phosphorus powder is placed in formation black phosphorus powder dispersion liquid in anaerobic water；
Optionally, the ph making this dispersion liquid is alkalescence；Preferably, black phosphorus powder is placed in the alkaline anaerobic aqueous solution, so that
The ph of described black phosphorus powder dispersion liquid is alkalescence；
(2) in an inert atmosphere, ultrasonic described black phosphorus powder dispersion liquid, preferably ultrasonic power are water bath sonicator or Probe Ultrasonic Searching；
(3) ultrasonic finish after, supernatant is collected by centrifugation, obtains described black phosphorus nanometer sheet.
2. preparation method according to claim 1, wherein:
Water bath sonicator described in step (2) is with 100～500w power ultrasonic 1～6h；Preferably, carried out using ultrasonic cleaning machine
Water bath sonicator；
Probe Ultrasonic Searching described in step (2) is to circulate to carry out in the way of working 1～10 second and stopping 1～10 second, the working time totally 1～
6h, power during work is 400～2000w；Preferably, described Probe Ultrasonic Searching is carried out using cell crushing instrument.
3. preparation method according to claim 1, wherein, the ph controlling described black phosphorus powder dispersion liquid in step (1) is 9
～12.
4. preparation method according to claim 3, wherein, step (1) is that black phosphorus powder is placed in the alkali that ph is 11～12
Property the anaerobic aqueous solution in formed black phosphorus powder dispersion liquid；Preferably, this alkaline anaerobic aqueous solution is Sodium Hydroxide Alkaline anaerobic water
Solution.
5. the preparation method according to any one of Claims 1 to 4, wherein, described in step (1), black phosphorus powder is to pass through
The grinding of black phosphorus bulk obtains；Preferably, the particle diameter of described black phosphorus powder is 10～1000 μm.
6. the preparation method according to any one of Claims 1 to 4, wherein, black phosphorus in described black phosphorus powder dispersion liquid
Concentration is 0.5～5mg/ml.
7. the preparation method according to any one of Claims 1 to 4, wherein, step (2), in ultrasonic procedure, controls institute
The temperature stating black phosphorus powder dispersion liquid is 0～30 DEG C；Preferably employ ice bath and control temperature.
8. the preparation method according to any one of Claims 1 to 4, wherein, step is collected by centrifugation supernatant described in (3)
It is to take supernatant dispersion liquid after centrifugation 10～60min under the conditions of rotating speed is 1000～5000rpm.
9. the black phosphorus nanometer sheet that the preparation method any one of claim 1～8 is obtained；Preferably, this black phosphorus nanometer sheet
Thickness be 1～20nm, lateral dimension be 20～500nm.
10. application in the photo-thermal therapy agent of preparation treating cancer for the black phosphorus nanometer sheet described in claim 9；Preferentially, will
Described black phosphorus nanometer sheet is configured to solution, and treating cancer under laser irradiates, it is highly preferred that black phosphorus nanometer sheet is configured to concentration
For solution more than 150 μ g/ml, it is 1w/cm in laser intensity2Under the conditions for the treatment of cancer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610680032.XA CN106335885B (en) | 2016-08-17 | 2016-08-17 | A kind of black phosphorus nanometer sheet and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610680032.XA CN106335885B (en) | 2016-08-17 | 2016-08-17 | A kind of black phosphorus nanometer sheet and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106335885A true CN106335885A (en) | 2017-01-18 |
| CN106335885B CN106335885B (en) | 2017-10-03 |
Family
ID=57825604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610680032.XA Active CN106335885B (en) | 2016-08-17 | 2016-08-17 | A kind of black phosphorus nanometer sheet and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106335885B (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106990144A (en) * | 2017-03-24 | 2017-07-28 | 福州大学 | Black phosphorus nanometer sheet and the preparation method for partly untiing carbon nano-fiber composite material |
| CN107007865A (en) * | 2017-05-05 | 2017-08-04 | 湖北大学 | A kind of chitosan black phosphorus composite aquogel and preparation method thereof |
| CN107119123A (en) * | 2017-05-09 | 2017-09-01 | 厦门大学 | A kind of method for improving PCR efficiency |
| CN107469082A (en) * | 2017-08-21 | 2017-12-15 | 中南大学 | A kind of application of black phosphorus nanometer sheet |
| CN107569683A (en) * | 2017-09-18 | 2018-01-12 | 深圳市人民医院 | Modified two-dimentional phosphorus of one kind and its preparation method and application |
| CN107602912A (en) * | 2017-08-15 | 2018-01-19 | 昆明理工大学 | A kind of nano-meter flame retardantses for high polymer material |
| CN107936266A (en) * | 2017-11-15 | 2018-04-20 | 深圳大学 | A kind of cellulose/black phosphorus nanometer sheet composite hydrogel and preparation method thereof |
| CN108275667A (en) * | 2017-12-11 | 2018-07-13 | 湖北中科墨磷科技有限公司 | A kind of black phosphorus material and the preparation method and application thereof of rare earth compounding modification |
| CN108284220A (en) * | 2017-12-26 | 2018-07-17 | 深圳大学 | A kind of bismuth alkene nanometer sheet and preparation method thereof |
| CN108976732A (en) * | 2018-06-04 | 2018-12-11 | 福州大学 | A method of improving black phosphorus nanometer sheet photo and thermal stability |
| WO2019024146A1 (en) * | 2017-08-04 | 2019-02-07 | 深圳先进技术研究院 | Black phosphorus/precious metal composite material, preparation method and application thereof |
| CN109455790A (en) * | 2018-11-27 | 2019-03-12 | 合肥工业大学 | A method of utilizing two-dimentional black phosphorus material efficient degradation organic pollutant |
| CN110280280A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Black phosphorus nanometer sheet, zinc sulphide/black phosphorus nanometer sheet preparation method and applications |
| CN110280281A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Zinc ferrite/black phosphorus microsphere compound preparation method and its application in photocatalysis field |
| CN110668412A (en) * | 2019-02-22 | 2020-01-10 | 中国科学院沈阳应用生态研究所 | Method for preparing black phosphorus nanosheet through low-temperature mediation |
| CN110755631A (en) * | 2019-11-27 | 2020-02-07 | 南昌大学 | Compound for quickly treating depression and preparation method and application thereof |
| CN110950313A (en) * | 2019-12-25 | 2020-04-03 | 深圳市中科墨磷科技有限公司 | Method for preparing polycrystalline black phosphorus nanosheets by hydrothermal etching method |
| CN110963504A (en) * | 2019-12-06 | 2020-04-07 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
| CN111137867A (en) * | 2018-11-06 | 2020-05-12 | 湖南工业大学 | Preparation method of surfactant-mediated few-layer black phosphorus nanosheet |
| CN111330655A (en) * | 2018-12-18 | 2020-06-26 | 深圳先进技术研究院 | Microfluidic chip for lipid compound detection and lipid compound detection method |
| CN111482618A (en) * | 2020-04-14 | 2020-08-04 | 西南林业大学 | Method for reducing and loading noble metal by black phosphorus nanosheet |
| CN112023956A (en) * | 2020-08-25 | 2020-12-04 | 陕西科技大学 | Black phosphorus alkene powder with high photocatalytic hydrogen production stability and preparation method thereof |
| CN112315977A (en) * | 2020-11-30 | 2021-02-05 | 南京大学 | Black phosphorus oxide nano material for osteoporosis |
| CN113318229A (en) * | 2021-06-01 | 2021-08-31 | 深圳大学 | Anti-tumor preparation based on black arsenic-phosphorus nanosheets and preparation method thereof |
| CN113425894A (en) * | 2020-03-23 | 2021-09-24 | 中国科学院深圳先进技术研究院 | Bone tissue engineering scaffold with gradual antibacterial and bone regeneration promoting functions and preparation method and application thereof |
| CN114452300A (en) * | 2020-11-09 | 2022-05-10 | 深圳先进技术研究院 | Application of black phosphorus nanosheet in preparation of drugs for inhibiting tumor migration and invasion |
| CN115463639A (en) * | 2022-10-28 | 2022-12-13 | 中船(邯郸)派瑞特种气体股份有限公司 | Nano black phosphorus-C 60 Preparation and application method of adsorbent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876199A (en) * | 2015-04-21 | 2015-09-02 | 合肥国轩高科动力能源股份公司 | Method for preparing few-layer black scales by ultrasonically stripping black scale |
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
| US20160126323A1 (en) * | 2014-10-10 | 2016-05-05 | Korea Basic Science Institute | Method of preparing monoatomic layer black phosphorous by irradiating ultrasound |
-
2016
- 2016-08-17 CN CN201610680032.XA patent/CN106335885B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160126323A1 (en) * | 2014-10-10 | 2016-05-05 | Korea Basic Science Institute | Method of preparing monoatomic layer black phosphorous by irradiating ultrasound |
| CN104876199A (en) * | 2015-04-21 | 2015-09-02 | 合肥国轩高科动力能源股份公司 | Method for preparing few-layer black scales by ultrasonically stripping black scale |
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN105535971A (en) * | 2015-12-22 | 2016-05-04 | 苏州大学 | A black phosphorus nanometer particle with biocompatibility, a preparing method thereof and applications of the black phosphorus nanometer particle |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106990144A (en) * | 2017-03-24 | 2017-07-28 | 福州大学 | Black phosphorus nanometer sheet and the preparation method for partly untiing carbon nano-fiber composite material |
| CN106990144B (en) * | 2017-03-24 | 2019-04-02 | 福州大学 | Black phosphorus nanometer sheet and the preparation method for partly unlocking carbon nano-fiber composite material |
| CN107007865A (en) * | 2017-05-05 | 2017-08-04 | 湖北大学 | A kind of chitosan black phosphorus composite aquogel and preparation method thereof |
| CN107119123A (en) * | 2017-05-09 | 2017-09-01 | 厦门大学 | A kind of method for improving PCR efficiency |
| WO2019024146A1 (en) * | 2017-08-04 | 2019-02-07 | 深圳先进技术研究院 | Black phosphorus/precious metal composite material, preparation method and application thereof |
| CN107602912A (en) * | 2017-08-15 | 2018-01-19 | 昆明理工大学 | A kind of nano-meter flame retardantses for high polymer material |
| CN107469082A (en) * | 2017-08-21 | 2017-12-15 | 中南大学 | A kind of application of black phosphorus nanometer sheet |
| CN107469082B (en) * | 2017-08-21 | 2021-04-16 | 中南大学 | Application of black phosphorus nanosheet |
| CN107569683A (en) * | 2017-09-18 | 2018-01-12 | 深圳市人民医院 | Modified two-dimentional phosphorus of one kind and its preparation method and application |
| CN107936266A (en) * | 2017-11-15 | 2018-04-20 | 深圳大学 | A kind of cellulose/black phosphorus nanometer sheet composite hydrogel and preparation method thereof |
| CN108275667A (en) * | 2017-12-11 | 2018-07-13 | 湖北中科墨磷科技有限公司 | A kind of black phosphorus material and the preparation method and application thereof of rare earth compounding modification |
| CN108275667B (en) * | 2017-12-11 | 2019-11-19 | 湖北中科墨磷科技有限公司 | A kind of black phosphorus material and the preparation method and application thereof of rare earth compounding modification |
| CN108284220A (en) * | 2017-12-26 | 2018-07-17 | 深圳大学 | A kind of bismuth alkene nanometer sheet and preparation method thereof |
| CN108976732A (en) * | 2018-06-04 | 2018-12-11 | 福州大学 | A method of improving black phosphorus nanometer sheet photo and thermal stability |
| CN111137867A (en) * | 2018-11-06 | 2020-05-12 | 湖南工业大学 | Preparation method of surfactant-mediated few-layer black phosphorus nanosheet |
| CN109455790A (en) * | 2018-11-27 | 2019-03-12 | 合肥工业大学 | A method of utilizing two-dimentional black phosphorus material efficient degradation organic pollutant |
| CN111330655A (en) * | 2018-12-18 | 2020-06-26 | 深圳先进技术研究院 | Microfluidic chip for lipid compound detection and lipid compound detection method |
| CN110668412A (en) * | 2019-02-22 | 2020-01-10 | 中国科学院沈阳应用生态研究所 | Method for preparing black phosphorus nanosheet through low-temperature mediation |
| CN110668412B (en) * | 2019-02-22 | 2023-03-21 | 中国科学院沈阳应用生态研究所 | Method for preparing black phosphorus nanosheet through low-temperature mediation |
| CN110280281A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Zinc ferrite/black phosphorus microsphere compound preparation method and its application in photocatalysis field |
| CN110280280A (en) * | 2019-07-31 | 2019-09-27 | 商丘师范学院 | Black phosphorus nanometer sheet, zinc sulphide/black phosphorus nanometer sheet preparation method and applications |
| CN110280281B (en) * | 2019-07-31 | 2022-01-28 | 商丘师范学院 | Preparation method of zinc ferrite/black phosphorus microsphere compound and application of zinc ferrite/black phosphorus microsphere compound in photocatalysis field |
| CN110280280B (en) * | 2019-07-31 | 2022-01-28 | 商丘师范学院 | Black phosphorus nanosheet, and preparation method and application of zinc sulfide/black phosphorus nanosheet |
| CN110755631A (en) * | 2019-11-27 | 2020-02-07 | 南昌大学 | Compound for quickly treating depression and preparation method and application thereof |
| CN110755631B (en) * | 2019-11-27 | 2023-03-14 | 南昌大学 | Compound for quickly treating depression as well as preparation method and application thereof |
| CN110963504B (en) * | 2019-12-06 | 2022-11-11 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
| CN110963504A (en) * | 2019-12-06 | 2020-04-07 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
| CN110950313A (en) * | 2019-12-25 | 2020-04-03 | 深圳市中科墨磷科技有限公司 | Method for preparing polycrystalline black phosphorus nanosheets by hydrothermal etching method |
| CN113425894A (en) * | 2020-03-23 | 2021-09-24 | 中国科学院深圳先进技术研究院 | Bone tissue engineering scaffold with gradual antibacterial and bone regeneration promoting functions and preparation method and application thereof |
| CN111482618A (en) * | 2020-04-14 | 2020-08-04 | 西南林业大学 | Method for reducing and loading noble metal by black phosphorus nanosheet |
| CN112023956A (en) * | 2020-08-25 | 2020-12-04 | 陕西科技大学 | Black phosphorus alkene powder with high photocatalytic hydrogen production stability and preparation method thereof |
| CN114452300A (en) * | 2020-11-09 | 2022-05-10 | 深圳先进技术研究院 | Application of black phosphorus nanosheet in preparation of drugs for inhibiting tumor migration and invasion |
| CN112315977A (en) * | 2020-11-30 | 2021-02-05 | 南京大学 | Black phosphorus oxide nano material for osteoporosis |
| CN113318229A (en) * | 2021-06-01 | 2021-08-31 | 深圳大学 | Anti-tumor preparation based on black arsenic-phosphorus nanosheets and preparation method thereof |
| CN115463639A (en) * | 2022-10-28 | 2022-12-13 | 中船(邯郸)派瑞特种气体股份有限公司 | Nano black phosphorus-C 60 Preparation and application method of adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106335885B (en) | 2017-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106335885B (en) | A kind of black phosphorus nanometer sheet and preparation method and application | |
| CN106267201A (en) | A kind of black phosphorus of polymer wrapped and preparation method and application | |
| Tang et al. | Pyroelectric nanoplatform for NIR-II-triggered photothermal therapy with simultaneous pyroelectric dynamic therapy | |
| Zhang et al. | Manganese carbonate nanoparticles‐mediated mitochondrial dysfunction for enhanced sonodynamic therapy | |
| Li et al. | Fluorine-containing graphene quantum dots with a high singlet oxygen generation applied for photodynamic therapy | |
| Guo et al. | Photothermal ablation cancer therapy using homogeneous Cs x WO 3 nanorods with broad near-infra-red absorption | |
| Zeng et al. | Multifunctional Fe 3 O 4–TiO 2 nanocomposites for magnetic resonance imaging and potential photodynamic therapy | |
| Chen et al. | Preparation and photodynamic therapy application of NaYF4: Yb, Tm–NaYF4: Yb, Er multifunctional upconverting nanoparticles | |
| Huang et al. | Controlled synthesis of upconverting nanoparticles/CuS yolk–shell nanoparticles for in vitro synergistic photothermal and photodynamic therapy of cancer cells | |
| CN105271174B (en) | Super carbon nano dot with strong near infrared absorption and preparation method and application | |
| Zhuang et al. | Solid‐phase synthesis of graphene quantum dots from the food additive citric acid under microwave irradiation and their use in live‐cell imaging | |
| CN104592993A (en) | Preparation method of carbon quantum dot and application thereof | |
| CN107343957B (en) | Black phosphorus/manganese dioxide composite nano material and preparation method and application thereof | |
| CN107936964A (en) | A kind of preparation method and applications of the nitrogen-doped graphene quantum dot of high selectivity | |
| Hallaji et al. | Recent advances in the rational synthesis of red-emissive carbon dots for nanomedicine applications: A review | |
| Wang et al. | Facile synthesis of hydrophilic polypyrrole nanoparticles for photothermal cancer therapy | |
| CN110339357A (en) | Copper ion doped carbon dots, preparation and its application as photosensitizer for photodynamic therapy | |
| CN106924734B (en) | Sea urchin-shaped-structure bismuth sulfide-cuprous sulfide heterojunction composite material and preparation method and application thereof | |
| CN108949151B (en) | Up-conversion luminescence nano composite material with transition metal disulfide growing on surface, preparation method and application | |
| Li et al. | Influence of silica surface coating on operated photodynamic therapy property of Yb3+-Tm3+: Ga (III)-doped ZnO upconversion nanoparticles | |
| Wei et al. | Orange-emissive carbon quantum dots for ligand-directed Golgi apparatus-targeting and in vivo imaging | |
| CN109589408A (en) | A kind of meter of shape liquid metal nanoparticle and its synthetic method and application | |
| CN104386665A (en) | Preparation method and bioapplication of single photon/double photon amorphous carbon dot | |
| CN109705316A (en) | The preparation method of artificial black cellulosic material with high photothermal conversion efficiency | |
| NL2026426B1 (en) | Fluorine-containing graphene quantum dots, preparation method and application thereof as photosensitiser for photodanamic therapy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |