CN107840332A - The efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications - Google Patents
The efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications Download PDFInfo
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- CN107840332A CN107840332A CN201711084169.XA CN201711084169A CN107840332A CN 107840332 A CN107840332 A CN 107840332A CN 201711084169 A CN201711084169 A CN 201711084169A CN 107840332 A CN107840332 A CN 107840332A
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Abstract
The efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications, belong to biological and pharmaceutical functionalization stock preparation field.Processing step is：A. use mixed acid pickling and clean nano-diamond powder suspension to neutrality with deionized water；B., the solution that nano-diamond powder and Lithium Aluminium Hydride are dissolved in tetrahydrofuran adds pyroreaction kettle inner bag to 60% the 90% of volume；C. closed high temperature reactor outer layer steel bushing is placed in heated at constant temperature case, and keeps constant temperature；D. after reaching soaking time, solution to be cooled after taking out reaction, hydrochloric acid is added, it with diamond and tetrahydrofuran reaction but is not used for dissolved metal ions；E. centrifuge and repeatedly deionized water cleaning nano-diamond powder to neutral anacidity remains；F. hydroxy terminal Nano diamond suspension is made in EtOH Sonicate cleaning after acetone cleaning, so as to obtain scattered pure high quality hydroxy terminal Nano diamond.The inventive method is convenient and simple, and reaction rate is fast, and the terminated of more Nano diamond powder can be realized under bulk solution in proportion.
Description
Technical field
The present invention relates to biological and pharmaceutical functionalization field of material preparation.Particularly hydroxy terminal diamond is further
The splendid starting point of diamond biological functional is realized, the high temperature high pressure enclosed vapour-liquid provided by pyroreaction kettle stirs ring certainly
Border, realize in the rapidly and efficiently safe formation hydroxy terminal of diamond surface, obtain the hydroxy terminal nanogold of discrete high quality
Hard rock.
Technical background
The diamond particles of nanoscale have excellent machinery and optical characteristics, and high surface area and surface texture are adjustable
Humorous property, and the nontoxic and biocompatibility of diamond cause Nano diamond to be had a wide range of applications in biological applications field
Prospect.Colloidal suspension prepared by Nano diamond discrete particle (single Nano diamond) has obtained in the nineties later stage
And deploy to study.Meanwhile safe and non-toxic fluorescence nano diamond has also turned under the semiconductor-quantum-point of bio-imaging field
Generation substitute.Nanoscale magnetic sensor based on Nano diamond is also developed.What is more important, using difference
Wet method or steam state chemical technology can cause the surface chemical reaction of Nano diamond make it that the excellent specific property of Nano diamond should
For other fields such as compound and medicine and biomolecule carriers.With the development of Nano diamond technology of preparing, make
It becomes biology imaging, medicine delivery, the application study focus of organizational project and medicine and pharmacology other field.Compared to it
His nano particle, Nano diamond have an outstanding feature, that is, the surface of diamond can make different function bases
Group is attached to diamond surface and achieves functionalization.For example, carboxy-terminal is formed by air or ozone in diamond surface
(-COOH)；Hydrogen terminal (- H) is formed by hydrogen plasma process；It is whole that fluorine is formed by halogen annealing or photochemical chlorination processing
End or chlorine terminal (- F or-Cl)；Different terminals such as ammonia terminal (- NH can be obtained by being heated in ammonia2) or nitrogen terminal
(C=N) etc..Different terminals has different characteristics and effect.Therefore, Suzanne Ciftan Hens
(Diamond.Relat.Mater.17,1858-1866, (2008)) have studied bioconjugate probe and nonspecific protein knot
Close and Shenderova O A (BIOINTERPHASES 10,3, (2015)) summary statement Nano diamond biology should
Surface science and engineering.Especially hydroxy terminal (- OH) can form long hydrocarbon chain by appropriate processing, group is conciliate in hydrocarbonylation
It is poly-, so that these special characteristics are applied to biological applications.The precursor terminal modified as biological functional, hydroxyl (-
OH) group is more than carboxyl (COOH) and oxygen terminal (- O) and hydrogen terminal (- H) in the energy of adsorption of diamond surface, is allowed to higher
At a temperature of or the hydrogenation of longer time can remove oh group, this indicates that hydroxy terminal has higher stability, from
And it ensure that hydroxyl surface terminal is not destroyed and is consistent during certain condition.Liang Y J and Anke
Krueger (ACS Nano, 3,2288-2296, (2009)) just proposes a kind of biotinylated generally mistake of Nano diamond
Journey, it is namely based on hydroxyl and forms organic micel terminal at room temperature by trimethyoxysilane, and passes through biotin and two
Chloroethanes, dimethyl aminopyridine and dichloromethane are from 0 DEG C to room temperature process to realize biotinylation.Diamond hydroxy terminal quilt
It is considered further to realize the splendid starting point of diamond biological functional.Therefore, it is how safe, efficiently realize diamond surface
Hydroxylating is also particularly important.Make diamond surface method for hydroxylation be to take a small amount of Nano diamond at present, and need to be placed in and not stop
The environmental protection of nitrogen is passed through, lasting stirring is up to tens of hours, neutral to solution PH subsequently through acidifying, then by alkalization,
Centrifugation, clean, it is dry etc. to obtain hydroxylating diamond nano powder.The PROCESS FOR TREATMENT diamond nano powder yields poorly, and process is slow,
It is poorly efficient, and venting process is easy to take out of toxicant.
The content of the invention
To solve the above problems, it is an object of the invention to propose a kind of quick, efficient and safe diamond surface hydroxyl
The method of base, so as to realize that, without gas shield, faster, preparation procedure is simpler for technical process, and solution concentration is lower, prepare
The higher diamond surface functional method of amount.Using preliminary cleaned nano-diamond powder is passed through, with Lithium Aluminium Hydride
The solution for being dissolved in tetrahydrofuran is sequentially added in pyroreaction kettle cavity, and closed high temperature reactor is placed in heated at constant temperature case,
Temperature is set to be higher than 66 DEG C.And diamond is set to pass through heated at constant temperature in the case where mixed solution vaporizes hyperbaric environment.Take out after cooling
Reaction solution, cleaned by dissolving with hydrochloric acid metal ion is added dropwise, and using deionized water for several times to solution neutral, then by acetone
And EtOH Sonicate ripple cleaning depolymerization, finally give hydroxy terminal Nano diamond powder sample.
The technical scheme is that：
A kind of efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications, it is characterised in that diamond
Powder realizes accelerated surface reaction to reach terminated under the confined space environment of solution boils high pressure.Without gas shield
And external force stirring, nanoparticle aggregate is avoided under stirring environment in vapour-liquid, high surface local concentration causes terminated with high temperature
Faster, effect is more preferable for process.Processing step is as follows：
(1) pickling processes of Nano diamond powder and cleaning
To remove Nano diamond powder surface metal inclusion that may be present, hydrocarbon, graphite etc..By nanogold
Hard rock powder sample is placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 1 hour to 2 hours, acid boils number as 2 to 5 times, rear to use
Deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in aeration cabinet
In with 60 DEG C to 200 DEG C aeration-drying 15 minutes to 2 hours.
(2) Nano diamond powder terminated environment is established
To ensure solution boils environment and pressure in reactor, 30g Nano diamond powder is arrived by 5, with 0.5-3mol/L
Lithium Aluminium Hydride be dissolved in tetrahydrofuran solution (Lithium Aluminium Hydride is dissolved in the solution prepared in tetrahydrofuran as solvent) stirring
Into suspension and together it is placed in reactor, ensures mixing suspension volume for 60% to the 90% of reactor volume.
(3) Nano diamond powder terminated process
Reactor is assembled, and capping kettle outer steel sleeve.Heated at constant temperature case is placed on afterwards, and temperature is set in four
More than 66 DEG C of hydrogen furans boiling temperature 80 DEG C to 200 DEG C.The timing since being reached design temperature, constant temperature time is set 1
By 10 hours.After constant temperature time terminates, treat that steel bushing temperature is reduced to room temperature, take out reactor inner bag and pour out suspension after reaction
To beaker.
(4) hydroxy terminal Nano diamond powder terminated subsequent treatment
Hydrochloric acid is added dropwise into reacted suspension, is down to 1 or so to PH and is equipped with stirring, with dissolution solvent
By lithium existing for reaction and aluminum metal element, reaction is avoided to separate out or adhere to.Afterwards 10 to 20 times are cleaned using deionized water extremely
Solution PH reaches neutral and centrifuged, to have the function that cleaning solvent solution mass.
(5) final process of hydroxy terminal Nano diamond powder
Acetone is added after the hydroxy terminal Nano diamond suspension that deionized water was cleaned is centrifuged, is cleaned by ultrasonic 3 to 5
It is secondary, to clean tetrahydrofuran and reacted organic substance residues.After also passing through centrifugation, ethanol is added, is cleaned by ultrasonic 3 to 5 times,
Final centrifugation taking-up is placed in aeration cabinet to be dried 30 minutes to 2 hours with 60 DEG C to 120 DEG C, obtains hydroxy terminal nanogold
Hard rock powder.
The key of implementation process of the present invention is：
(1) Nano diamonds powder due to grain diameter it is small, specific surface area is big, the factor such as preparation process, it is necessary to repeatedly it is more
The pickling and cleaning of amount, to ensure the cleaning of diamond, ensure the purity of diamond, avoid remaining metal ion or impurity
Substitute into.
(2) the surface-functionalized process of diamonds in a kettle needs certain solvent strength, to ensure in gold
Hard rock surface has enough functional groups to form hydroxy terminal in the environment of reactor provides.When powder addition is few,
Solvent can be reduced accordingly；When amount of powder is big, Lithium Aluminium Hydride quantity of solvent need to rise therewith, and solvent strength is from 0.5 to 3mol/
L, in the reactor of different size, keep concentration constant, need to only increase and decrease amount of solution and amount of powder on year-on-year basis, ensure to receive per 1g weight
The Lithium Aluminium Hydride that rice diamond corresponds to 0.1mol/L and concentrations above is dissolved in the solution of tetrahydrofuran (Lithium Aluminium Hydride is molten as solvent
The solution prepared in tetrahydrofuran).
(3) in a kettle, the solution that diamond and Lithium Aluminium Hydride are dissolved in tetrahydrofuran matches somebody with somebody the liquid measure of mixing suspension to
The minimum scale 60% that reactor volume need to be maintained at arrives highest rate 90%, and volume ratio shared by suspension is applied to different rule
The reactor of lattice.The ratio is comparatively fast carried out to the reaction of assurance function.
(4) is during heated at constant temperature, to ensure the hyperbaric environment of hydroxy terminal process, when accounted for liquor capacity
When reactor volume is smaller, higher temperature need to be used；When solution account for volume ratio it is higher when, need to suitably reduce heating-up temperature.
(5) holding temperatures must assure that more than 66 DEG C of the boiling point in tetrahydrofuran (THF), and the limit is born less than reactor
Temperature.To ensure that the vapour-liquid in the confined space of reactor flows, accelerate to play a part of class stirring while reaction, realize
Quick motion of the Nano diamond particle under vapour-liquid environment, avoids depositing and polymerize, and accelerates reaction rate.
(6) diabatic process certain because pyroreaction kettle has, it is when in heated at constant temperature case chamber that need to ensure soaking time
Temperature starts timing after reaching 15 minutes of required temperature.
(7) in the subsequent treatment after pyroreactions, the strong acid for dissolving ion must use hydrochloric acid, to ensure
Do not reacted in metal process is dissolved with tetrahydrofuran.
(8) to ensure not introduce new impurity and cleaning process, deionized water need to be used to clean 10 to 20 times and coordinate from
Heart process, until solution PH to neutrality to reach the cleaning of acid and metal ion, if diamond dust amount is more or every gram herein
Diamond corresponds to solvent strength ratio and is higher than 0.1mol/L, and deionized water wash number need to rise to 20 times；Third must be used afterwards
Ketone is cleaned by ultrasonic 3 to 5 times, to have the function that organic matter after the remaining tetrahydrofuran of cleaning and reaction.
The compared to the prior art possessed beneficial effect of the present invention is：
(1) realizes hydroxy terminal using reactor, and course of reaction is in confined space, is continually fed into and carries without nitrogen
For protection, while avoid taking out of for toxic component so that this method is safer simpler.
(2) realizes hydroxy terminal using reactor, and course of reaction is in hot environment.Heating-up temperature is above solvent
The boiling point of tetrahydrofuran (THF), do not only have high temperature compared to the mode of magnetic agitation under normal temperature, in process of the invention and provide more
Energy needed for fast reaction, it is often more important that the magnetic agitation that not only instead of from agitaion of vapour-liquid environment makes bortz powder
End keeps motion, and can be effectively prevented from the aggregation of Nano diamond, makes the course of reaction speed faster.
(3) realizes hydroxy terminal, the height that course of reaction is in high-temperature expansion and evaporation conditions are formed using reactor
Pressure ring border, this, compared to high surface part solvent strength under condition of normal pressure, is formed on Nano diamond powder surface, to shorten
Molecular motion free path, molecular motion speed is improved, accelerates the formation of hydroxy terminal, not only makes the course of reaction speed faster,
The density of hydroxy terminal can be improved simultaneously.Realize hydroxy terminal using reactor, have due to during high temperature, high pressure,
High local concentrationses and high vapour-liquid movement rate so that more Nano diamond powder can be realized under bulk solution in proportion
Terminated.
(4) equally can use using the high temperature high pressure enclosed vapour-liquid that reactor provides in high temperature environments from the effect stirred
In the surface-functionalized or surface treatment of polycrystalline diamond and single-crystal diamond；And Buddha's warrior attendant is realized using different solution systems
The different types of functionalization in stone surface.
Brief description of the drawings
Fig. 1 is the SEM photograph and cleaning precipitation process photo of Nano diamond after functionalization of the present invention.
Fig. 2 is the Fourier transform infrared collection of illustrative plates of present invention gained hydroxy terminal diamond dust after the different disposal time
(FTIR)。
Fig. 3 is the Fourier transform infrared collection of illustrative plates of the high quality hydroxy terminal Nano diamond powder obtained by the present invention
(FTIR)。
Embodiment
Embodiment one
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 15 minutes is sequentially placed into acetone soln and absolute ethyl alcohol again, is placed in logical
Obtain within 2 hours drying pure Nano diamond powder with 60 DEG C of aeration-dryings in wind drying box.(2) by 5g nano-diamond powders
End, the solution that tetrahydrofuran is dissolved in 0.5mol/L Lithium Aluminium Hydride stir into suspension and are together placed in reactor, ensure
Mixing suspension volume is the 80% of reactor volume.(3) reactor is assembled, and capping kettle outer steel sleeve.Afterwards by it
Heated at constant temperature case is placed in, temperature is set 100 DEG C.The timing since being reached design temperature, constant temperature time was set at 1 hour.It is permanent
After the warm time terminates, treat that steel bushing temperature is reduced to room temperature, take out reactor inner bag and pour out suspension after reaction to beaker.To anti-
Hydrochloric acid is added dropwise in suspension after answering, is down to 1 or so to PH and is equipped with stirring.10 times are cleaned to molten using deionized water afterwards
Liquid PH reaches neutral and centrifuged, to have the function that cleaning solvent solution mass.(5) hydroxy terminal for cleaning deionized water
Acetone is added after the centrifugation of Nano diamond suspension, is cleaned by ultrasonic 5 times, it is residual to clean tetrahydrofuran and reacted organic matter
Stay.After also passing through centrifugation, ethanol is added, is cleaned by ultrasonic 5 times, final centrifugation taking-up is placed in aeration cabinet with 60 DEG C of dryings
2 hours, obtain hydroxy terminal Nano diamond powder.The SEM pictures of gained sample are as shown in figure 1, and Fourier transform infrared
Spectrogram is as shown in Figure 2.
Embodiment two
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in
Obtain within 1 hour drying pure Nano diamond powder with 100 DEG C of aeration-dryings in aeration cabinet.(2) by 10g nanometer Buddha's warrior attendants
Stone powder, the solution that tetrahydrofuran is dissolved in 1mol/L Lithium Aluminium Hydride stir into suspension and are together placed in reactor, protect
Demonstrate,prove 80% that mixing suspension volume is reactor volume.(3) reactor is assembled, and capping kettle outer steel sleeve.Afterwards will
It is placed in heated at constant temperature case, and temperature is set into 100 DEG C.The timing since being reached design temperature, constant temperature time was set at 2 hours.
After constant temperature time terminates, treat that steel bushing temperature is reduced to room temperature, take out reactor inner bag and pour out suspension after reaction to beaker.To
Hydrochloric acid is added dropwise in reacted suspension, is down to 1 or so to PH and is equipped with stirring.Afterwards 10 times are cleaned using deionized water extremely
Solution PH reaches neutral and centrifuged, to have the function that cleaning solvent solution mass.(5) hydroxyl for cleaning deionized water is whole
Acetone is added after the Nano diamond suspension centrifugation of end, is cleaned by ultrasonic 5 times, it is residual to clean tetrahydrofuran and reacted organic matter
Stay.After also passing through centrifugation, ethanol is added, is cleaned by ultrasonic 5 times, final centrifugation taking-up is placed in aeration cabinet with 60 DEG C of dryings
2 hours, obtain hydroxy terminal Nano diamond powder.The SEM pictures of gained sample are consistent with Fig. 1, and Fourier transform infrared
Spectrogram is as shown in Figure 2.
Embodiment three
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in
Obtain within 15 minutes drying pure Nano diamond powder with 200 DEG C of aeration-dryings in aeration cabinet.(2) by 15g nanogold
Hard rock powder, the solution that tetrahydrofuran is dissolved in 2mol/L Lithium Aluminium Hydride stir into suspension and are together placed in reactor,
Ensure 80% that mixing suspension volume is reactor volume.(3) reactor is assembled, and capping kettle outer steel sleeve.Afterwards
Heated at constant temperature case is placed on, temperature is set 100 DEG C.The timing since being reached design temperature, set constant temperature time small 4
When.After constant temperature time terminates, treat that steel bushing temperature is reduced to room temperature, take out reactor inner bag and pour out suspension after reaction to burning
Cup.Hydrochloric acid is added dropwise into reacted suspension, is down to 1 or so to PH and is equipped with stirring.Cleaned afterwards using deionized water
Reach neutral to solution PH and centrifuge for 20 times, to have the function that cleaning solvent solution mass.(5) deionized water was cleaned
Acetone is added after the centrifugation of hydroxy terminal Nano diamond suspension, is cleaned by ultrasonic 5 times, to clean tetrahydrofuran and reacted have
Machine thing remains.After also passing through centrifugation, add ethanol, be cleaned by ultrasonic 5 times, it is final centrifuge taking-up be placed in aeration cabinet with
100 DEG C of dryings 1 hour.The SEM pictures of gained sample are consistent with Fig. 1, and Fourier transform infrared spectroscopy figure such as Fig. 2.The technique
The Fourier transform infrared spectroscopy figure of resulting high quality hydroxy terminal Nano diamond powder is as shown in figure 3, in 1000cm-1
Left and right and 3600cm-1 or so are-OH keys peak, are-OH keys the peak of absorption water at 1603cm-1 and 3410cm-1, in 1300cm-
1 or so is C-O keys peak, provable C-OH presence herein, and each peak is clear, and intensity is high, suggests the formation of the hydroxyl of high quality
Terminal.
Embodiment four
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in
With 100 DEG C of aeration-drying 1 hour in aeration cabinet.(2) it is molten with 3mol/L Lithium Aluminium Hydride by 15g Nano diamond powder
Suspension is stirred into the solution of tetrahydrofuran and is together placed in reactor, ensures that mixing suspension volume is reactor volume
70%.(3) reactor is assembled, and capping kettle outer steel sleeve.Heated at constant temperature case is placed on afterwards, and temperature is set
150℃.The timing since being reached design temperature, constant temperature time was set at 6 hours.After constant temperature time terminates, treat that steel bushing temperature drops
For room temperature, take out reactor inner bag and pour out suspension after reaction to beaker.Salt is added dropwise into reacted suspension
Acid, it is down to 1 or so to PH and is equipped with stirring.Cleaned afterwards using deionized water and reach neutral to solution PH 20 times and centrifuge, with up to
To the effect of cleaning solvent solution mass.(5) after the hydroxy terminal Nano diamond suspension centrifugation cleaned deionized water
Acetone is added, is cleaned by ultrasonic 5 times, to clean tetrahydrofuran and reacted organic substance residues.After also passing through centrifugation, second is added
Alcohol, it is cleaned by ultrasonic 5 times, final centrifugation taking-up is placed in aeration cabinet to be dried 1 hour with 100 DEG C, obtains hydroxy terminal nanometer
Diamond dust.It is consistent shown in the SEM pictures and Fig. 1 of gained sample, and Fourier transform infrared spectroscopy figure is as shown in Fig. 2 simultaneously
It is similar to Fig. 3.
Embodiment five
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in
With 100 DEG C of aeration-drying 1 hour in aeration cabinet.(2) it is molten with 3mol/L Lithium Aluminium Hydride by 20g Nano diamond powder
Suspension is stirred into the solution of tetrahydrofuran and is together placed in reactor, ensures that mixing suspension volume is reactor volume
60%.(3) reactor is assembled, and capping kettle outer steel sleeve.Heated at constant temperature case is placed on afterwards, and temperature is set
200℃.The timing since being reached design temperature, constant temperature time was set at 6 hours.After constant temperature time terminates, treat that steel bushing temperature drops
For room temperature, take out reactor inner bag and pour out suspension after reaction to beaker.Salt is added dropwise into reacted suspension
Acid, it is down to 1 or so to PH and is equipped with stirring.Cleaned afterwards using deionized water and reach neutral to solution PH 20 times and centrifuge, with up to
To the effect of cleaning solvent solution mass.(5) after the hydroxy terminal Nano diamond suspension centrifugation cleaned deionized water
Acetone is added, is cleaned by ultrasonic 5 times, to clean tetrahydrofuran and reacted organic substance residues.After also passing through centrifugation, second is added
Alcohol, it is cleaned by ultrasonic 5 times, final centrifugation taking-up is placed in aeration cabinet to be dried 30 minutes with 120 DEG C, obtains hydroxy terminal nanometer
Diamond dust.Shown in the SEM pictures and Fig. 1 of gained sample unanimously, and Fourier transform infrared spectroscopy figure is similar to Fig. 3.
Embodiment six
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 15 minutes is sequentially placed into acetone soln and absolute ethyl alcohol again, is placed in logical
With 100 DEG C of aeration-drying 1 hour in wind drying box.(2) by 30g Nano diamond powder, it is dissolved in 3mol/L Lithium Aluminium Hydride
The solution of tetrahydrofuran stirs into suspension and is together placed in reactor, ensures mixing suspension volume for reactor volume
90%.(3) reactor is assembled, and capping kettle outer steel sleeve.Heated at constant temperature case is placed on afterwards, and temperature is set 80
℃.The timing since being reached design temperature, constant temperature time was set at 6 hours.After constant temperature time terminates, treat that steel bushing temperature is reduced to room
Temperature, take out reactor inner bag and pour out suspension after reaction to beaker.Hydrochloric acid is added dropwise into reacted suspension, extremely
PH is down to 1 or so and is equipped with stirring.Use deionized water to clean 20 times afterwards to reach neutral to solution PH and centrifuge, to reach cleaning
The effect of solvent solution material.(5) third is added after the hydroxy terminal Nano diamond suspension that deionized water was cleaned is centrifuged
Ketone, it is cleaned by ultrasonic 5 times, to clean tetrahydrofuran and reacted organic substance residues.After also passing through centrifugation, ethanol is added, is surpassed
Sound is cleaned 5 times, and final centrifugation taking-up is placed in aeration cabinet to be dried 30 minutes with 120 DEG C, obtains hydroxy terminal nanometer Buddha's warrior attendant
Stone powder.Shown in the SEM pictures and Fig. 1 of gained sample unanimously, and Fourier transform infrared spectroscopy figure is similar to Fig. 3.
Embodiment seven
(1) 100nm diamond dust samples are taken to be placed in HCl：H2SO4=1：Boiled in 5 mixed liquor 2 hours, acid boils number
For 3 times, after use deionized water rinsing；Each ultrasonic cleaning 10-15 minutes are sequentially placed into acetone soln and absolute ethyl alcohol again, are placed in
With 100 DEG C of aeration-drying 1 hour in aeration cabinet.(2) it is molten with 3mol/L Lithium Aluminium Hydride by 30g Nano diamond powder
Suspension is stirred into the solution of tetrahydrofuran and is together placed in reactor, ensures that mixing suspension volume is reactor volume
80%.(3) reactor is assembled, and capping kettle outer steel sleeve.Heated at constant temperature case is placed on afterwards, and temperature is set
100℃.The timing since being reached design temperature, constant temperature time was set at 10 hours.After constant temperature time terminates, treat that steel bushing temperature drops
For room temperature, take out reactor inner bag and pour out suspension after reaction to beaker.Salt is added dropwise into reacted suspension
Acid, it is down to 1 or so to PH and is equipped with stirring.Use deionized water to clean 10 to 20 times afterwards to reach neutral to solution PH and centrifuge,
To have the function that cleaning solvent solution mass.(5) by the hydroxy terminal Nano diamond suspension that deionized water was cleaned from
Acetone is added after the heart, is cleaned by ultrasonic 5 times, to clean tetrahydrofuran and reacted organic substance residues.After also passing through centrifugation, add
Enter ethanol, be cleaned by ultrasonic 5 times, final centrifugation taking-up is placed in aeration cabinet to be dried 30 minutes with 120 DEG C, obtains hydroxy terminal
Nano diamond powder.It is consistent shown in the SEM pictures and Fig. 1 of gained sample, and Fourier transform infrared spectroscopy figure and Fig. 3 phases
Seemingly.
Claims (5)
- A kind of 1. efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications, it is characterised in that bortz powder Accelerated surface reaction is realized to reach terminated, processing step is as follows in end under the confined space environment of solution boils high pressure：(1) pickling processes of Nano diamond powder and cleaningTo remove Nano diamond powder surface metal inclusion that may be present, hydrocarbon, graphite, by nano-diamond powder Last sample is placed in HCl：H2SO4A period of time is boiled in mixed liquor, afterwards with deionized water rinsing, then is sequentially placed into acetone soln It is cleaned by ultrasonic with absolute ethyl alcohol, is placed in aeration-drying in aeration cabinet；(2) Nano diamond powder terminated environment is establishedTo ensure solution boils environment and pressure in reactor, Nano diamond powder is placed in Lithium Aluminium Hydride and is dissolved in tetrahydrofuran Solution (Lithium Aluminium Hydride is dissolved in the solution prepared in tetrahydrofuran as solvent), form suspension by stirring and together put In reactor, ensure mixing suspension volume for 60% to the 90% of reactor volume；(3) Nano diamond powder terminated processReactor is assembled, and capping kettle outer steel sleeve, heated at constant temperature case is placed on afterwards, and temperature is set in tetrahydrochysene furan The above certain temperature constant temperature of 66 DEG C of boiling temperature of muttering is for a period of time；After constant temperature time terminates, treat that steel bushing temperature is reduced to room temperature, take Go out reactor inner bag and pour out suspension after reaction to beaker；(4) hydroxy terminal Nano diamond powder terminated subsequent treatmentHydrochloric acid is added dropwise into reacted suspension, is down to 1 to PH and is equipped with stirring, is reacted with passing through in dissolution solvent Existing lithium and aluminum metal element, reaction is avoided to separate out or adhere to；10 to 20 times are cleaned to solution PH using deionized water afterwards Reach neutral and centrifuge, to have the function that cleaning solvent solution mass；(5) final process of hydroxy terminal Nano diamond powderAcetone is added after the hydroxy terminal Nano diamond suspension that deionized water was cleaned is centrifuged, is cleaned by ultrasonic, with cleaning Tetrahydrofuran and reacted organic substance residues, after also passing through centrifugation, ethanol is added, is cleaned by ultrasonic again, final centrifuging and taking Go out to be placed in and a period of time is dried in aeration cabinet, obtain hydroxy terminal Nano diamond powder.
- 2. a kind of efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications as claimed in claim 1, its It is characterised by step (1) described HCl：H2SO4Ratio be 1：5, boiling time 1 hour to 2 hours, acid boils number as 2 to 5 times； Respectively it is cleaned by ultrasonic 10-15 minutes, 60 DEG C to 200 DEG C of aeration cabinet drying temperature in acetone soln and absolute ethyl alcohol, ventilation is done Dry 15 minutes to the 2 hours time.
- 3. a kind of efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications as claimed in claim 1, its It is characterised by that the Nano diamond powder of step (2) the 5-30g weight is dissolved in four with the Lithium Aluminium Hydride of 0.5-3mol/L concentration The solution mixing of hydrogen furans, Lithium Aluminium Hydride are dissolved in the solution prepared in tetrahydrofuran as solvent, need to ensure every 1g weight Diamond dust is correspondingly equal to or higher than 0.1mol/L Lithium Aluminium Hydride in the solution concentration of tetrahydrofuran.
- 4. a kind of efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications as claimed in claim 1, its It is characterised by that the thermostat temperature of step (3) the heated at constant temperature case is set in above 80 DEG C of 66 DEG C of tetrahydrofuran boiling temperature To 200 DEG C；The timing since being reached design temperature, constant temperature time was set at 1 to 10 hours.
- 5. a kind of efficient terminated preparation method of the hydroxy terminal Nano diamond of biologic applications as claimed in claim 1, its It is characterised by that step (5) number that is cleaned by ultrasonic is 3 to 5 times, to clean tetrahydrofuran and reacted organic substance residues, together Sample is after centrifugation, and ultrasonic cleaning number is also 3 to 5 times after adding ethanol, and aeration cabinet temperature 60 C is dried to 120 DEG C 30 minutes to 2 hours time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110342509A (en) * | 2019-07-26 | 2019-10-18 | 曹郁 | A kind of hydroxyl Nano diamond for preparing the method for hydroxyl Nano diamond using new and effective reducing agent red aluminum and its being prepared |
| CN111333066A (en) * | 2020-03-14 | 2020-06-26 | 严仙荣 | Nano-diamond surface silicification method |
| CN114302742A (en) * | 2019-08-13 | 2022-04-08 | 密苏里大学管委会 | Depolymerization of nanodiamond particles |
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| US20160075561A1 (en) * | 2014-09-12 | 2016-03-17 | National Tsing Hua University | Thiolation method for modifying nanodiamonds |
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| US20160075561A1 (en) * | 2014-09-12 | 2016-03-17 | National Tsing Hua University | Thiolation method for modifying nanodiamonds |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342509A (en) * | 2019-07-26 | 2019-10-18 | 曹郁 | A kind of hydroxyl Nano diamond for preparing the method for hydroxyl Nano diamond using new and effective reducing agent red aluminum and its being prepared |
| CN110342509B (en) * | 2019-07-26 | 2021-04-23 | 曹郁 | Method for preparing hydroxyl nano-diamond by using efficient reducing agent red aluminum and hydroxyl nano-diamond prepared by method |
| CN114302742A (en) * | 2019-08-13 | 2022-04-08 | 密苏里大学管委会 | Depolymerization of nanodiamond particles |
| CN111333066A (en) * | 2020-03-14 | 2020-06-26 | 严仙荣 | Nano-diamond surface silicification method |
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