CN105536659A - 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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- CN105536659A CN105536659A CN201610010033.3A CN201610010033A CN105536659A CN 105536659 A CN105536659 A CN 105536659A CN 201610010033 A CN201610010033 A CN 201610010033A CN 105536659 A CN105536659 A CN 105536659A
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- shape microballoon
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- 239000004005 microsphere Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 22
- 230000004043 responsiveness Effects 0.000 title abstract 3
- 239000002159 nanocrystal Substances 0.000 claims abstract description 10
- 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 21
- 239000000243 solution Substances 0.000 claims description 21
- 230000002441 reversible effect Effects 0.000 claims description 14
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 230000000638 stimulation Effects 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
- 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 10
- 230000008859 change 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
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 230000008569 process Effects 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
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect 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
- 238000013270 controlled release Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process 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
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000002371 ultraviolet--visible spectrum 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.More specifically, a kind of vesica shape Nano microsphere with pH response and preparation method thereof is related to.
Background technology
In numerous nanostructureds, nanocapsule blister microballoon has potential application prospect due to the hollow-core construction of its uniqueness multi-field.The nanocapsule blister microballoon be made up of inorganic nanoparticles (as Au, CuS, CdSe etc.), due to the intergranular effect of intercoupling of nanometer module units, has important application prospect in fields such as catalysis, drug delivery and bio-imagings.In recent years, outside stimulus response vesica constantly emerges in large numbers, for further controllable adjustment drug delivery provides possibility.Up to the present, existing large quantifier elimination is used for Co ntrolled release about the inorganic nano vesica shape microballoon of pH response, thermal response and photoresponse.
Publication number is: the Chinese invention patent of 103920433A discloses a kind of vesica shape microballoon, and hydrogen and stability are produced in the catalysis that this microballoon has had, the enhancing effect had in the test of surface plasma Raman.By the mode of optical drive, inorganic nano-crystal is assembled into vesica shape microballoon in its preparation method, illumination makes nano grain surface part: the C with mercapto functional group
6-12mercaptan, 7-(12-sulfydryl dodecyloxy)-2 hydrogen-chromen-2-one or 4-(12-sulfydryl dodecyloxy) azobenzene sulfydryl end there is oxidation and form hydrophilic sulfonic acid groups, come off from nano grain surface, under solvent action, anti-plug enters nano grain surface, sulfonic group outside, formed amphipathic with first wife's body, realize assembling.But assemble the vesica shape microballoon obtained and not there is pH response, and this assembling is irreversible, cannot be used in Co ntrolled release.
Based on following two aspects, controlled release still has the space that can promote and improve.On the one hand, the assembling of inorganic nano vesica shape microballoon and de-assembly depend on the organic response part being modified at its surface, such as PEG, and azobenzene etc. all need complicated organic synthesis step.On the other hand, the self assembling process of nano particle is normally irreversible.At present, reversible assembling form can only be between mono-dispersed nano particle and random aggregation, does not also have the report of reversible assembling between nano particle and nanocapsule blister microballoon.
Therefore, the inorganic nano vesica shape microballoon realizing reversible assembling developing the modification of a kind of commercialization ligand molecular is a challenge.
Summary of the invention
One object of the present invention is to provide a kind of vesica shape microballoon with pH response, and this vesica shape microballoon has pH response, under soda acid stimulates, realize reversible assembling.
Another object of the present invention is to provide a kind of preparation method with the vesica shape microballoon of pH response.This preparation method is simple, and manufacturing conditions is gentle, by selecting modified ligand 4-mercaptobenzoic acid specific and cheap and easy to get and preparation method, makes the vesica shape microballoon obtained have pH response, under soda acid stimulates, realize reversible assembling.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
There is a vesica shape microballoon for pH response, obtained by nanocrystalline the assembling under ultrasound-driven of Au; Described vesica shape microballoon has many shell structurres; The diameter of described vesica shape microballoon is 20-200nm; The nanocrystalline size of described Au is 1-10nm; Described vesica shape microballoon has pH response, under soda acid stimulates, realize reversible assembling.
Preferably, the described method realizing reversible assembling under soda acid stimulates is: after 1) adding the NaOH solution of 1M in the aqueous solution of described vesica shape microballoon, and vesica shape microballoon de-assembly forms mono-dispersed nano particle; 2), after adding the HCl solution of 2M in the mono-dispersed nano particle aqueous solution, mono-dispersed nano particle is assembled and is obtained vesica shape microballoon.
Preferably, step 1) and step 2) can repetitive cycling carry out.
Preferably, step 1) addition of described NaOH solution is the 2-10 μ L/mL vesica shape microballoon aqueous solution; Step 2) addition of described HCl solution is the 2.5-12.5 μ L/mL mono-dispersed nano particle aqueous solution.
For reaching above-mentioned second object, the present invention adopts following technical proposals:
There is a preparation method for the vesica shape microballoon of pH response, comprise the steps:
A) in Au nanocrystal surface, 4-mercaptobenzoic acid in modification;
B) by step a) in modified Au nanocrystalline under ultrasound condition in a solvent assembling obtain the vesica shape Nano microsphere with pH response.
Preferably, step a) in, described modification refer to utilize ultrasonic or stir 4-mercaptobenzoic acid is applied to Au nanocrystal surface, replace original part.Described original part can be selected from the hydrophobic ligand such as oleyl amine.
Preferably, step b) in, described ultrasound condition is ultrasonic 10-60min.
Preferably, step b) in, described solvent is selected from water or ethanol.
Preferably, reaction is carried out all at normal temperatures.
Preferably, step b) diameter with the vesica shape microballoon of pH response that obtains is 20-200nm, has many shell structurres; Described vesica shape microballoon has pH response, under soda acid stimulates, realize reversible assembling.
The vesica shape microballoon of a kind of pH of having response of the present invention can be applicable to the field such as catalysis, Co ntrolled release.In catalytic field, vesica shape microballoon and dispersed nano particle have different catalytic performances, can be regulated and controled the carrying out of reaction by the pH value of regulation system.In Co ntrolled release field, vesica shape microballoon can coated organic molecule discharging in alkaline pH environment, and the nano particle dissociated can realize release by coated organic molecule again.
Beneficial effect of the present invention is as follows:
The assemble method of vesica shape microballoon provided by the invention is ultrasound-driven, and the method is simple, utilizes the 4-mercaptobenzoic acid of commercialization cheapness as part, simple and easy to get, and preparation condition is gentle.
Vesica shape microballoon provided by the invention has pH response, utilizes business-like 4-mercaptobenzoic acid to realize pH response as part, does not need to synthesize the pH response molecule with special construction.
The invention provides the character of the reversible assembling of inorganic nano vesica shape microballoon, the inorganic nanoparticles after dissociating can be assembled into vesica shape microballoon again.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Figure 1A illustrates the transmission electron microscope photo of many shells vesica shape microballoon of the gold nanocrystals assembling preparation that embodiment 1 ultrasound-driven 4-mercaptobenzoic acid is modified.
Figure 1B illustrates the size distribution plot of the vesica shape microballoon of the gold nanocrystals assembling preparation that embodiment 1 ultrasound-driven 4-mercaptobenzoic acid is modified.
Fig. 2 illustrates that the gold nanocrystals that embodiment 1 ultrasound-driven 4-mercaptobenzoic acid is modified is assembled into the infrared spectrogram of vesica shape microballoon and the infrared spectrogram of 4-mercaptobenzoic acid and oleyl amine.
Fig. 3 illustrates that embodiment 1 vesica shape microballoon de-assembly is the transmission electron microscope picture of monodispersed gold nano grain.
Fig. 4 illustrates the ultraviolet-visible light spectrogram of the monodisperse gold particle of embodiment 1 vesica shape microballoon and de-assembly.
Fig. 5 illustrates that in embodiment 1, de-assembly is the transmission electron microscope picture that monodispersed gold nano grain is assembled into vesica shape microballoon again.
Fig. 6 illustrates the ultraviolet-visible spectrum absworption peak variation diagram of the gold nano grain repeatedly adding the de-assembly that NaOH and HCl causes in embodiment 1 and the vesica shape microballoon assembled again.
Fig. 7 illustrates the transmission electron microscope picture of the gold nano grain repeatedly adding the de-assembly that NaOH and HCl causes in embodiment 1 and the vesica shape microballoon assembled again: Fig. 7 A is the transmission electron microscope picture of the vesica shape microballoon that embodiment 1 prepares; Fig. 7 B is the gold nano grain transmission electron microscope picture of first time de-assembly; Fig. 7 C is the transmission electron microscope picture of the vesica shape microballoon that first time assembles again; Fig. 7 D-Fig. 7 I is followed successively by the transmission electron microscope picture continuing repetition 3 de-assembly and assemble gains again.
Fig. 8 A to illustrate in embodiment 2 after the coated rhodamine molecule of gold nano vesica, dissociates in the basic conditions and discharges the fluorescence spectrum figure of rhodamine molecule.
After Fig. 8 B illustrates and dissociates in embodiment 2, gold nano grain assembles coated rhodamine molecule again, the fluorescence spectrum figure of secondary release under alkali condition.
Detailed description of the invention
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
There is a preparation method for the vesica shape microballoon of pH response, comprise the steps:
Under room temperature, be the ethanolic solution of the 50 μ L4-mercaptobenzoic acids of 6mM by concentration, join surface by the ethanolic solution of the 3nm gold nano grain of oleyl amine molecular modification, wherein the quality of gold nano grain is 0.4mg, and volumes of aqueous ethanol is 2mL.Mixture is after ultrasonic process 30min, and it is centrifugal to add about 5mL benzinum.Gained solid dispersal in 2mL water, then through ultrasonic process 30min, obtains the vesica shape microballoon with pH response.
The obtained vesica shape microballoon transmission electron microscope with pH response is characterized, Figure 1A is the transmission electron microscope photo obtaining vesica shape microballoon, Figure 1B is the size distribution plot obtaining vesica shape microballoon, can find out that vesica shape microballoon is of a size of 89.2 ± 16.8nm, have multilayer shell-like structure.
Infrared spectrum analysis is carried out to the obtained vesica shape microballoon with pH response, as shown in Figure 2.Find that vesica shape microsphere surface is simultaneously containing 4-mercaptobenzoic acid and oleyl amine two kinds of parts, namely exists hydrophilic and hydrophobic two kinds of parts simultaneously.
Under room temperature, be that the NaOH solution of 1M adds in the vesica shape microballoon aqueous solution of acquisition by 5 μ L/mL by concentration, and characterize with transmission electron microscope, as shown in Figure 3, vesica shape microballoon is dissociated into monodispersed Au nano particle.
Carry out uv-visible absorption spectra analysis to the vesica shape microballoon of assembling and the Au nano particle of de-assembly, as shown in Figure 4, vesica shape microballoon ultraviolet-ray visible absorbing peak is positioned at 545nm, and after being dissociated into single dispersing Au nano particle, its absworption peak is blue shifted to 513nm.
Under room temperature, HCl solution concentration being about 2M by 6.25 μ L/mL add dissociate after in monodispersed Au nano particle, again obtain vesica shape microballoon through assembling, centrifuged pellet is dispersed in 2mL water again.
Carry out transmission electron microscope sign to the above-mentioned vesica shape microballoon assembling gained again, as shown in Figure 5, the vesica shape microballoon obtained does not have significant change.
Repeat above-mentioned vesica shape microballoon and be dissociated into monodispersed Au nano particle and monodispersed Au nano particle through assembling the step 3 time again obtaining vesica shape microballoon again, and after adding NaOH or HCl, carry out transmission electron microscope and uv-visible absorption spectra characterizes at every turn.Sum up uv-visible absorption spectra absworption peak variation diagram as shown in Figure 6, the ultraviolet-ray visible absorbing peak position of golden vesica shape microballoon remains near 530nm, and the gold nano grain absworption peak after dissociating is positioned at 510nm, and has the trend of continuous blue shift.Transmission electron microscope photo is gathered, as shown in Figure 7, there is not significant change with the follow-up gold nano vesica pattern assembled again in that assembles, repeatedly golden vesica shape microballoon all presents monodispersed state after dissociating, and illustrates that this golden vesica shape microballoon has the character of good reversible assembling.
Embodiment 2
Repeat pH response vesica shape microballoon preparation process in embodiment 1, its difference is that centrifugal rear gained solid dispersal is in the rhodamine aqueous solution.In the vesica shape microspheres solution obtained, add the NaOH solution of 5mM, and measure its fluorescence spectrum.Rhodamine is as a kind of fluorescence molecule, and when being encapsulated by gold nano vesica, almost do not have fluorescence in solution, along with NaOH solution adds, imitated vesicle structure dissociates, and rhodamine molecule is released, Fluorescence Increasing in solution.As shown in Figure 8 A, along with adding of NaOH solution, in solution, fluorescence increases with NaOH addition and strengthens until no longer change gradually, indicates the release of rhodamine molecule completely.
Again be dispersed in the rhodamine aqueous solution by gold nano grain after dissociating, add HCl, gold nano grain is again assembled and is formed vesica shape microballoon, and is encapsulated by rhodamine molecule.Add the NaOH solution of 5mM, measure its fluorescence spectrum.As shown in Figure 8 B, rhodamine secondary releasing trend is identical with first time, increases and strengthen gradually, until no longer change with NaOH addition.
Comparative example 1
Be that the NaOH solution of 1M adds publication number by the amount of 5 μ L/mL and is by concentration: in the Chinese invention patent embodiment gained vesica shape microballoon of 103920433A, characterize with transmission electron microscope, vesica shape microballoon does not dissociate, and cannot realize reversible assembling.
Comparative example 2
Changing the 4-mercaptobenzoic acid in the preparation process of vesica shape microballoon in embodiment 1 into publication number is: the C in the Chinese invention patent of 103920433A
6-12mercaptan, 7-(12-sulfydryl dodecyloxy)-2 hydrogen-chromen-2-one or 4-(12-sulfydryl dodecyloxy) azobenzene, other conditions are constant, cannot obtain vesica shape microballoon.
Comparative example 3
By in the preparation method of vesica shape microballoon in embodiment 1, " gained solid dispersal in 2mL water, then through ultrasonic process 30min " is changed into and " by gained solid dispersal in 2mL toluene, then being squeezed in 3.6mL acetone.Mixture uses ultraviolet light immediately, and ultraviolet wavelength is 300-400nm, and illumination is about 30min in atmosphere, passes into condensed water simultaneously, and maintenance system temperature is room temperature ", other condition is constant, cannot form vesica shape microballoon.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. have a vesica shape microballoon for pH response, it is characterized in that, described vesica shape Nano microsphere is obtained by nanocrystalline the assembling under ultrasound-driven of Au; Described vesica shape microballoon has many shell structurres; The diameter of described vesica shape microballoon is 20-200nm; The nanocrystalline size of described Au is 1-10nm; Described vesica shape microballoon has pH response, under soda acid stimulates, realize reversible assembling.
2. the vesica shape microballoon with pH response according to claim 1, it is characterized in that, the described method realizing reversible assembling under soda acid stimulates is: after 1) adding the NaOH solution of 1M in the aqueous solution of described vesica shape microballoon, and vesica shape microballoon de-assembly forms mono-dispersed nano particle; 2), after adding the HCl solution of 2M in the mono-dispersed nano particle aqueous solution, mono-dispersed nano particle is assembled and is obtained vesica shape microballoon.
3. the vesica shape microballoon with pH response according to claim 2, is characterized in that, step 1) and step 2) can repetitive cycling carry out.
4. the vesica shape microballoon with pH response according to claim 2, is characterized in that, step 1) addition of described NaOH solution is the 2-10 μ L/mL vesica shape microballoon aqueous solution; Step 2) addition of described HCl solution is the 2.5-12.5 μ L/mL mono-dispersed nano particle aqueous solution.
5. the preparation method with the vesica shape microballoon of pH response as described in any one of claim 1-4, is characterized in that, comprise the steps:
A) in Au nanocrystal surface, 4-mercaptobenzoic acid in modification;
B) by step a) in modified Au nanocrystalline under ultrasound condition in a solvent assembling obtain the vesica shape Nano microsphere with pH response.
6. preparation method according to claim 5, is characterized in that, step a) in, described modification refer to utilize ultrasonic or stir 4-mercaptobenzoic acid is applied to Au nanocrystal surface, replace original part.
7. preparation method according to claim 5, is characterized in that, step b) in, described ultrasound condition is ultrasonic 10-60min.
8. preparation method according to claim 5, is characterized in that, step b) in, described solvent is selected from water or ethanol.
9. preparation method according to claim 5, is characterized in that, reaction is carried out all at normal temperatures.
10. preparation method according to claim 5, is characterized in that, step b) diameter with the vesica shape microballoon of pH response that obtains is 20-200nm, has many shell structurres; Described vesica shape microballoon has pH response, under soda acid stimulates, realize reversible assembling.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108788180A (en) * | 2018-07-06 | 2018-11-13 | 山东大学 | A kind of optical property is controllable and the preparation method of the Ag aggregates of nanoparticles of the reversible assembling of pH response dynamics |
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| 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 |
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