CN105536659B - Vesicular microspheres with pH responsiveness and preparation method thereof - Google Patents
Vesicular microspheres with pH responsiveness and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000004005 microsphere Substances 0.000 title abstract description 7
- 230000004043 responsiveness Effects 0.000 title abstract 3
- 239000002159 nanocrystal Substances 0.000 claims abstract description 10
- 230000000638 stimulation Effects 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 230000004044 response Effects 0.000 claims description 35
- 239000002105 nanoparticle Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical group OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000002441 reversible effect Effects 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002775 capsule Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 230000003252 repetitive effect Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 18
- 229910052737 gold Inorganic materials 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 15
- 235000013339 cereals Nutrition 0.000 description 15
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- -1 dodecyloxy Chemical group 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002088 nanocapsule Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a vesicular microsphere with pH responsiveness, which is obtained by assembling Au nanocrystals under ultrasonic drive, and is of a multi-shell structure, the diameter of the vesicular microsphere is 20-200nm, and the size of the Au nanocrystals is 1-10 nm. The vesicle-shaped microsphere has rapid pH responsiveness, and can be reversibly assembled under acid-base stimulation. The vesicle-shaped microsphere is simple and easy to obtain, and can be used in the fields of catalysis, drug release and the like.
Description
Technical field
The present invention relates to the preparation field of nano material.Received more particularly, to a kind of vesica shape with pH responses
Meter Wei Qiu and preparation method thereof.
Background technology
In numerous nanostructureds, nanocapsule blister microballoon is due to its unique hollow-core construction and multi-field with latent
Application prospect.The nanocapsule blister microballoon being made up of inorganic nanoparticles (such as Au, CuS, CdSe etc.), because nanometer assembles
The effect of intercoupling between unit grain, there is important application prospect in fields such as catalysis, drug delivery and bio-imagings.
In recent years, outside stimulus response vesica is constantly emerged in large numbers, and possibility is provided for further controllable adjustment drug delivery.To current
Untill, existing substantial amounts of research is released on the inorganic nano vesica shape microballoon of pH responses, thermal response and photoresponse for control
Put.
Publication No.：103920433A Chinese invention patent discloses a kind of vesica shape microballoon, what the microballoon had had
Catalysis production hydrogen and stability, the enhancing effect having had in the test of surface plasma Raman.Pass through in its preparation method
Inorganic nano-crystal is assembled into vesica shape microballoon by the mode of optical drive, and illumination makes nano grain surface part：With Mercaptofunctional
The C of group6-12Mercaptan, 7- (12- sulfydryls dodecyloxy) -2 hydrogen-chromen-2-ones or 4- (12- sulfydryls dodecyloxy)
Azobenzene sulfydryl end occurs oxidation and forms hydrophilic sulfonic acid groups, is come off from nano grain surface, anti-plug enters to receive under solvent action
Rice grain surface, sulfonic group outside, form amphipathic, realization assembling with first wife's body.But assemble obtained vesica shape microballoon not have
There are pH responses, and this assembling is irreversible, is not used in control release.
Based on following two aspects, controlled release still have can be lifted and improved space.On the one hand, inorganic nano vesica
The assembling of shape microballoon is required for de-assembly dependent on organic response part of the modification on its surface, such as PEG, azobenzene etc.
Complicated organic synthesis step.On the other hand, the self assembling process of nano particle is typically irreversible.At present, reversible group
Dress form can only be between mono-dispersed nano particle and random aggregation, it is also micro- without nano particle and nanocapsule blister
The report of reversible assembling between ball.
Therefore, developing a kind of inorganic nano vesica shape microballoon for the achievable reversible assembling for being commercialized ligand molecular modification is
One challenge.
The content of the invention
It is an object of the present invention to provide a kind of vesica shape microballoon with pH responses, the vesica shape microballoon has
PH responses, reversible assembling is realized under soda acid stimulation.
It is another object of the present invention to provide a kind of preparation method of the vesica shape microballoon with pH responses.The system
Preparation Method is simple, and manufacturing conditions are gentle, by selecting specific and cheap and easy to get modified ligand 4- mercaptobenzoic acids and preparation
Method so that obtained vesica shape microballoon has pH responses, and reversible assembling is realized under soda acid stimulation.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of vesica shape microballoon with pH responses, is obtained by nanocrystalline assembled under ultrasound-driven of Au；The vesica
Shape microballoon has more shell structurres；A diameter of 20-200nm of the vesica shape microballoon；The size nanocrystalline Au is 1-
10nm；The vesica shape microballoon has pH responses, and reversible assembling is realized under soda acid stimulation.
Preferably, it is described to realize that the method for reversible assembling is under soda acid stimulation：1) to the water-soluble of the vesica shape microballoon
After adding 1M NaOH solution in liquid, vesica shape microballoon de-assembly forms mono-dispersed nano particle；2) to mono-dispersed nano
After adding 2M HCl solution in the particle aqueous solution, mono-dispersed nano particle assembles to obtain vesica shape microballoon again.
Preferably, step 1) and the repeatable circulation of step 2) are carried out.
Preferably, the addition of the step 1) NaOH solution is the 2-10 μ L/mL vesica shape microballoon aqueous solution；Step 2) institute
The addition for stating HCl solution is the 2.5-12.5 μ L/mL mono-dispersed nano particle aqueous solution.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of the vesica shape microballoon with pH responses, comprises the following steps：
A) the 4- mercaptobenzoic acids in Au nanocrystal surfaces, modification；
B) nanocrystalline assembled in a solvent under ultrasound condition of the Au through modification in step a) is obtained with pH responses
Vesica shape nanoparticle.
Preferably, in step a), the modification refers to 4- mercaptobenzoic acids are applied into Au nanometers using ultrasound or stirring
Brilliant surface, substitute original part.Original part may be selected from the hydrophobic ligands such as oleyl amine.
Preferably, in step b), the ultrasound condition is ultrasonic 10-60min.
Preferably, in step b), the solvent is selected from water or ethanol.
Preferably, reaction is carried out at normal temperatures.
Preferably, a diameter of 20-200nm for the vesica shape microballoon with pH responses that step b) is obtained, has more shells
Rotating fields；The vesica shape microballoon has pH responses, and reversible assembling is realized under soda acid stimulation.
A kind of vesica shape microballoon with pH responses of the present invention can be applied to the fields such as catalysis, control release.It is being catalyzed
In terms of field, vesica shape microballoon and dispersed nano particle have different catalytic performances, can pass through the pH value of regulation system
To regulate and control the progress of reaction.In terms of control release field, vesica shape microballoon can coat organic molecule and in alkaline pH environment
Release, the nano particle of dissociation can coat organic molecule again and realize release.
Beneficial effects of the present invention are as follows：
The assemble method of vesica shape microballoon provided by the invention is ultrasound-driven, and this method is simple, cheap using commercialization
4- mercaptobenzoic acids as part, simple and easy to get, preparation condition is gentle.
Vesica shape microballoon provided by the invention has pH responses, real by the use of commercialized 4- mercaptobenzoic acids as part
Existing pH responses, it is not necessary to pH response molecule of the synthesis with special construction.
The present invention provides the property of the reversible assembling of inorganic nano vesica shape microballoon, and the inorganic nanoparticles after dissociation can be again
It is secondary to be assembled into vesica shape microballoon.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Figure 1A shows more shell vesicas prepared by the gold nanocrystals assembling of the ultrasound-driven 4- mercaptobenzoic acids of embodiment 1 modification
The transmission electron microscope photo of shape microballoon.
Figure 1B shows vesica shape microballoon prepared by the gold nanocrystals assembling of the ultrasound-driven 4- mercaptobenzoic acids of embodiment 1 modification
Size distribution plot.
Fig. 2 shows that the gold nanocrystals of the ultrasound-driven 4- mercaptobenzoic acids of embodiment 1 modification are assembled into the red of vesica shape microballoon
External spectrum figure and the infrared spectrogram of 4- mercaptobenzoic acids and oleyl amine.
Fig. 3 shows the transmission electron microscope picture that the vesica shape microballoon de-assembly of embodiment 1 is monodispersed gold nano grain.
Fig. 4 shows the UV-visible spectrum of the vesica shape microballoon of embodiment 1 and the monodisperse gold particle of de-assembly.
Fig. 5 shows that de-assembly in embodiment 1 is the transmission electricity that monodispersed gold nano grain is assembled into vesica shape microballoon again
Mirror figure.
The capsule that Fig. 6 shows the gold nano grain of de-assembly caused by adding NaOH and HCl repeatedly in embodiment 1 and assembled again
The ultraviolet-visible spectrum absworption peak variation diagram of blister microballoon.
The capsule that Fig. 7 shows the gold nano grain of de-assembly caused by adding NaOH and HCl repeatedly in embodiment 1 and assembled again
The transmission electron microscope picture of blister microballoon：Fig. 7 A are the transmission electron microscope picture for the vesica shape microballoon that embodiment 1 is prepared；Fig. 7 B are first
The gold nano grain transmission electron microscope picture of secondary de-assembly；Fig. 7 C are the transmission electron microscope picture of the vesica shape microballoon assembled again for the first time；Figure
7D- Fig. 7 I are followed successively by the transmission electron microscope picture for continuing to be repeated 3 times de-assembly and assemble gains again.
After Fig. 8 A show that gold nano vesica coats rhodamine molecule in embodiment 2, dissociate in the basic conditions and discharge sieve
The fluorescence spectra of red bright molecule.
Fig. 8 B show that gold nano grain assembles cladding rhodamine molecule again after being dissociated in embodiment 2, secondary under alkalescence condition
The fluorescence spectra of release.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of preparation method of the vesica shape microballoon with pH responses, comprises the following steps：
At room temperature, the ethanol solution by concentration for 6mM 50 μ L 4- mercaptobenzoic acids, is added to surface by oleyl amine molecule
In the ethanol solution of the 3nm gold nano grains of modification, wherein the quality of gold nano grain is 0.4mg, and volumes of aqueous ethanol is
2mL.After the sonicated 30min of mixture, the centrifugation of about 5mL petroleum ethers is added.Gained solid is scattered in 2mL water, then is passed through
30min is ultrasonically treated, obtains the vesica shape microballoon with pH responses.
The obtained vesica shape microballoon with pH responses is characterized with transmission electron microscope, Figure 1A is to obtain vesica shape microballoon
Transmission electron microscope photo, Figure 1B are the size distribution plot for obtaining vesica shape microballoon, it can be seen that the size of vesica shape microballoon is 89.2
± 16.8nm, there is multilayer shell-like structure.
Infrared spectrum analysis is carried out to the obtained vesica shape microballoon with pH responses, as shown in Figure 2.It was found that vesica shape
Microsphere surface contains two kinds of parts of 4- mercaptobenzoic acids and oleyl amine simultaneously, i.e., hydrophilic and hydrophobic two kinds of parts be present simultaneously.
At room temperature, the NaOH solution that concentration is 1M is added in the vesica shape microballoon aqueous solution obtained by 5 μ L/mL, be used in combination
Transmission electron microscope characterizes, as shown in figure 3, vesica shape microballoon is dissociated into monodispersed Au nano particles.
The Au nano particles of vesica shape microballoon and de-assembly to assembling carry out uv-visible absorption spectra analysis, such as Fig. 4
Shown, vesica shape microballoon ultraviolet-ray visible absorbing peak is located at 545nm, and after being dissociated into single dispersing Au nano particles, its absworption peak is blue
Move to 513nm.
At room temperature, the HCl solution that concentration is about 2M is added to monodispersed Au nano particles after dissociating by 6.25 μ L/mL
In, vesica shape microballoon is retrieved through assembling again, centrifuged pellet is dispersed in 2mL water.
Transmission electron microscope sign is carried out to the above-mentioned vesica shape microballoon for assembling gained again, as shown in figure 5, resulting vesica shape
Microballoon does not have significant change.
Repeat above-mentioned vesica shape microballoon and be dissociated into monodispersed Au nano particles and monodispersed Au nano particles through group again
Dress retrieves the step 3 time of vesica shape microballoon, and carries out transmission electron microscope and ultraviolet-visible after NaOH or HCl is added every time
Absorption spectrum characterizes.Summarize uv-visible absorption spectra absworption peak variation diagram as shown in fig. 6, golden vesica shape microballoon it is ultraviolet-can
See that absorbing peak position is maintained near 530nm, and the gold nano grain absworption peak after dissociating is located at 510nm, and have continuous blue shift
Trend.Transmission electron microscope photo is collected, as shown in fig. 7, the gold nano vesica pattern assembled again assemble and follow-up is not sent out
Raw significant change, monodispersed state is repeatedly presented after golden vesica shape microballoon dissociation, illustrate the golden vesica shape microballoon have compared with
The property of good reversible assembling.
Embodiment 2
PH response vesica shape microballoon preparation processes in embodiment 1 are repeated, its difference is after centrifuging that gained solid disperses
In the rhodamine aqueous solution.5mM NaOH solution is added into obtained vesica shape microspheres solution, and determines its fluorescence spectrum.
Rhodamine when being encapsulated by gold nano vesica, does not almost have fluorescence as a kind of fluorescence molecule in solution, with NaOH solution plus
Enter, imitated vesicle structure dissociation, rhodamine molecule is released, Fluorescence Increasing in solution.As shown in Figure 8 A, adding with NaOH solution
Enter, fluorescence increases with NaOH additions and gradually strengthened up to no longer changing in solution, indicates that rhodamine molecule discharges
Completely.
Gold nano grain after dissociation is dispersed again in the rhodamine aqueous solution, adds HCl, gold nano grain group again
Dress forms vesica shape microballoon, and rhodamine molecule is encapsulated.5mM NaOH solution is added, determines its fluorescence spectrum.Such as Fig. 8 B institutes
Show, the secondary releasing trend of rhodamine is identical with first time, increases with NaOH additions and gradually strengthens, until no longer changing.
Comparative example 1
The NaOH solution that concentration is 1M is added into Publication No. by 5 μ L/mL amount：103920433A Chinese invention is special
In vesica shape microballoon obtained by sharp embodiment, characterized with transmission electron microscope, vesica shape microballoon does not dissociate, and can not realize reversible group
Dress.
Comparative example 2
Change the 4- mercaptobenzoic acids in the preparation process of vesica shape microballoon in embodiment 1 into Publication No.：
C in 103920433A Chinese invention patent6-12Mercaptan, 7- (12- sulfydryls dodecyloxy) -2 hydrogen-chromene -2-
Ketone or 4- (12- sulfydryls dodecyloxy) azobenzene, other conditions are constant, can not obtain vesica shape microballoon.
Comparative example 3
In the preparation method of vesica shape microballoon in embodiment 1, will incite somebody to action " gained solid is scattered in 2mL water, then by ultrasound
Processing 30min " is changed to " gained solid is scattered in 2mL toluene, then squeezed into 3.6mL acetone.Mixture is used immediately
Ultraviolet light, ultraviolet light wave a length of 300-400nm, in atmosphere illumination about 30min, while be passed through condensed water, keep system temperature
For room temperature ", other conditions are constant, can not form vesica shape microballoon.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (10)
- A kind of 1. vesica shape microballoon with pH responses, it is characterised in that the vesica shape nanoparticle by Au it is nanocrystalline Assembling obtains under ultrasound-driven；The vesica shape microballoon has more shell structurres；A diameter of 20- of the vesica shape microballoon 200nm；The size nanocrystalline Au is 1-10nm；The vesica shape microballoon has pH responses, is realized under soda acid stimulation Reversible assembling；Wherein, the Au nanocrystal surfaces are modified with 4- mercaptobenzoic acids.
- 2. the vesica shape microballoon according to claim 1 with pH responses, it is characterised in that described under soda acid stimulation The method for realizing reversible assembling is：1) after adding 1M NaOH solution into the aqueous solution of the vesica shape microballoon, vesica shape is micro- Ball de-assembly forms mono-dispersed nano particle；2) it is single after adding 2M HCl solution into the mono-dispersed nano particle aqueous solution Scattered nano particle assembles to obtain vesica shape microballoon again.
- 3. the vesica shape microballoon according to claim 2 with pH responses, it is characterised in that step 1) and step 2) can Repetitive cycling is carried out.
- 4. the vesica shape microballoon according to claim 2 with pH responses, it is characterised in that the step 1) NaOH is molten The addition of liquid is the 2-10 μ L/mL vesica shape microballoon aqueous solution；The addition of the step 2) HCl solution is 2.5-12.5 μ L/ The mL mono-dispersed nano particle aqueous solution.
- 5. the preparation method of the vesica shape microballoon with pH responses as described in claim any one of 1-4, it is characterised in that Comprise the following steps：A) the 4- mercaptobenzoic acids in Au nanocrystal surfaces, modification；B) nanocrystalline assembled in a solvent under ultrasound condition of the Au through modification in step a) is obtained into the capsule with pH responses Blister nanoparticle.
- 6. preparation method according to claim 5, it is characterised in that in step a), it is described modification refer to using ultrasound or 4- mercaptobenzoic acids are applied to Au nanocrystal surfaces by stirring, substitute original part.
- 7. preparation method according to claim 5, it is characterised in that in step b), the ultrasound condition is ultrasonic 10- 60min。
- 8. preparation method according to claim 5, it is characterised in that in step b), the solvent is selected from water or ethanol.
- 9. preparation method according to claim 5, it is characterised in that reaction is carried out at normal temperatures.
- 10. preparation method according to claim 5, it is characterised in that the vesica with pH responses that step b) is obtained A diameter of 20-200nm of shape microballoon, there are more shell structurres；The vesica shape microballoon has pH responses, under soda acid stimulation Realize reversible assembling.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108788180B (en) * | 2018-07-06 | 2024-07-19 | 山东大学 | Preparation method of Ag nano particle aggregate with controllable optical properties and pH response and dynamic reversible assembly |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003087287A1 (en) * | 2002-04-10 | 2003-10-23 | Salvona L.L.C. | Targeted controlled delivery compositions activated by changes in ph or salt concentration |
| CN102649036A (en) * | 2012-05-15 | 2012-08-29 | 北京大学 | Environment-sensitive polymer hollow microsphere and preparation method thereof |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
| CN104001484A (en) * | 2014-05-26 | 2014-08-27 | 齐鲁工业大学 | Preparation method of pH responsiveness polyphenol amine microcapsules |
| CN104927418A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Acid-alkali dual response intelligent nano container based anti-corrosion coating preparation method and application |
-
2016
- 2016-01-08 CN CN201610010033.3A patent/CN105536659B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003087287A1 (en) * | 2002-04-10 | 2003-10-23 | Salvona L.L.C. | Targeted controlled delivery compositions activated by changes in ph or salt concentration |
| CN102649036A (en) * | 2012-05-15 | 2012-08-29 | 北京大学 | Environment-sensitive polymer hollow microsphere and preparation method thereof |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
| CN104001484A (en) * | 2014-05-26 | 2014-08-27 | 齐鲁工业大学 | Preparation method of pH responsiveness polyphenol amine microcapsules |
| CN104927418A (en) * | 2015-07-06 | 2015-09-23 | 江苏固格澜栅防护设施有限公司 | Acid-alkali dual response intelligent nano container based anti-corrosion coating preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108788180B (en) * | 2018-07-06 | 2024-07-19 | 山东大学 | Preparation method of Ag nano particle aggregate with controllable optical properties and pH response and dynamic reversible assembly |
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