CN105968245B - Particle size-adjustable aldehyde-containing nano-microsphere with core-shell structure and preparation method thereof - Google Patents
Particle size-adjustable aldehyde-containing nano-microsphere with core-shell structure and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 66
- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 34
- 239000004005 microsphere Substances 0.000 title abstract description 17
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 127
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 89
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical group C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000014897 Streptococcus lactis Nutrition 0.000 claims abstract description 27
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 26
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 17
- 241000194035 Lactococcus lactis Species 0.000 claims abstract 6
- 239000002105 nanoparticle Substances 0.000 claims description 73
- 239000000839 emulsion Substances 0.000 claims description 53
- 239000006210 lotion Substances 0.000 claims description 48
- 239000003995 emulsifying agent Substances 0.000 claims description 45
- 239000003999 initiator Substances 0.000 claims description 43
- 238000004132 cross linking Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 210000000481 breast Anatomy 0.000 claims description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000011257 shell material Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000011806 microball Substances 0.000 claims 1
- 125000003172 aldehyde group Chemical group 0.000 abstract 4
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- 244000057717 Streptococcus lactis Species 0.000 description 21
- 229920006280 packaging film Polymers 0.000 description 9
- 239000012785 packaging film Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 108010053775 Nisin Proteins 0.000 description 5
- NVNLLIYOARQCIX-MSHCCFNRSA-N Nisin Chemical compound N1C(=O)[C@@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H]([C@H](C)CC)NC(=O)[C@@H](NC(=O)C(=C/C)/NC(=O)[C@H](N)[C@H](C)CC)CSC[C@@H]1C(=O)N[C@@H]1C(=O)N2CCC[C@@H]2C(=O)NCC(=O)N[C@@H](C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(NCC(=O)N[C@H](C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCSC)C(=O)NCC(=O)N[C@H](CS[C@@H]2C)C(=O)N[C@H](CC(N)=O)C(=O)N[C@H](CCSC)C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(N[C@H](C)C(=O)N[C@@H]3C(=O)N[C@@H](C(N[C@H](CC=4NC=NC=4)C(=O)N[C@H](CS[C@@H]3C)C(=O)N[C@H](CO)C(=O)N[C@H]([C@H](C)CC)C(=O)N[C@H](CC=3NC=NC=3)C(=O)N[C@H](C(C)C)C(=O)NC(=C)C(=O)N[C@H](CCCCN)C(O)=O)=O)CS[C@@H]2C)=O)=O)CS[C@@H]1C NVNLLIYOARQCIX-MSHCCFNRSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004309 nisin Substances 0.000 description 5
- 235000010297 nisin Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- -1 After quick stirring Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 240000000203 Salix gracilistyla Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005199 ultracentrifugation Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- DHEJIZSVHGOKMJ-UHFFFAOYSA-N 2-ethenylbenzaldehyde Chemical compound C=CC1=CC=CC=C1C=O DHEJIZSVHGOKMJ-UHFFFAOYSA-N 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004317 lacrimation Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses an aldehyde-containing nano microsphere with an adjustable particle size and a core-shell structure, wherein the particle size of the aldehyde-containing nano microsphere is 100-305 nm, the dispersity is 0.1-0.202, a core monomer of the aldehyde-containing nano microsphere is styrene, a shell monomer is 4-vinylbenzaldehyde, or the shell monomer is a mixed monomer of styrene and 4-vinylbenzaldehyde, the mass part ratio of the core monomer to the shell monomer is 4:1, and the aldehyde-containing nano microsphere is adjustable in particle size and good in dispersity. The invention also discloses an aldehyde group-containing nano microsphere-streptococcus lactis conjugate which is prepared from the aldehyde group-containing nano microsphere and streptococcus lactis, wherein the aldehyde group in the aldehyde group-containing nano microsphere is coupled with the amino group in the streptococcus lactis, so that the high-temperature inactivation of the streptococcus lactis can be avoided, and the stability of the streptococcus lactis is enhanced.
Description
Technical field
The invention belongs to core-shell emulsion technical field, and in particular to a kind of particle diameter is adjustable to contain aldehyde radical with core shell structure
Nanoparticle and preparation method thereof.
Background technology
Functional polymer containing aldehyde radical have the advantages that it is general, flexible, easy to use, it is particularly noticeable.Contain aldehyde radical at present
Monomer mainly has three kinds：Methacrylaldehyde, 4- vinylbenzaldehydes (VBA) and various substituted 4- vinyl bigcatkin willow aldehydes (IVDG).
Wherein, wherein methacrylaldehyde as monomer obtain polymer microballoon be it is most common be also it is most, but monomer toxicity is big, explosive
It is fried, lacrimation is strong, limit it and further apply.2007, wool professors and professor Lu Jiang reported 4- vinyl benzenes respectively
Formaldehyde (Macromolecules, 2007,40：793~795) and ferrocene substitution 4- vinyl bigcatkin willow aldehydes
(Macromolecules, 2007,40：1891~1896), and by RAFT it polymerize, obtains the clear and definite aldehyde-containing polymer of structure
Thing, compare the 4- vinyl bigcatkin willow aldehydes with substituent, and the synthesis step of VBA monomers is simple, yield higher, therefore, closely
The birds of the same feather flock together research of compound of Nian Lai, VBA receives much concern, but obtains the regulatable 4- vinylbenzaldehydes of particle diameter by emulsion polymerization and gather
Compound nanoparticle has no its report.
After bioactive molecule is conjugated with functional polymer, it can effectively improve its dissolubility, stability, activity and add
Work performance, can also strengthen the performances such as its compatibility sometimes.Therefore in recent years Polymer-bioactive molecular conjugate in medicine, raw
Thing science and technology and nano science field cause extensive concern.Streptococcus lactis (Ninsin) can by human body enzyme degraded,
Digestion, is a kind of efficient, safe and nontoxic, without side-effects antiseptics for natural food.But there is presently no particle diameter is regulatable
The research of aspect is mutually conjugated with streptococcus lactis (Ninsin) for 4- vinylbenzaldehydes polymer nano-microspheres.
The content of the invention
First technical problem to be solved by this invention is how to provide a kind of particle diameter adjustable containing with core shell structure
Aldehyde radical nanoparticle, it is adjustable that this contains aldehyde radical nanoparticle particle size, good dispersion degree.
Second technical problem to be solved by this invention is to provide that above-mentioned particle diameter is adjustable to contain aldehyde with core shell structure
The preparation method of based nanospheres.
3rd technical problem to be solved by this invention is to provide a kind of nanoparticle containing aldehyde radical-streptococcus lactis and is conjugated
Thing and preparation method thereof, this contains aldehyde radical nanoparticle-streptococcus lactis conjugate by by the aldehyde radical in nanoparticle containing aldehyde radical
Mutually it is coupled with the amino in streptococcus lactis, is avoided that the high temperature deactivation of streptococcus lactis, strengthens its stability.
First technical problem to be solved by this invention is achieved through the following technical solutions：A kind of particle diameter is adjustable
The nanoparticle containing aldehyde radical with core shell structure, which is 100~305nm, dispersion degree 0.1
~0.202, the nuclear monomer of the nanoparticle containing aldehyde radical is styrene, and shell monomer is 4- vinylbenzaldehydes, or shell monomer is
The proportion by weight of both the mix monomer of styrene and 4- vinylbenzaldehydes, the nuclear monomer and the shell monomer is 4:1.
Second technical problem to be solved by this invention is achieved through the following technical solutions：Above-mentioned particle diameter is adjustable
The nanoparticle containing aldehyde radical with core shell structure the preferable preparation method of one of which, comprise the following steps：
(1) core lotion and shell lotion are prepared：Core lotion is made of nuclear monomer, cross-linking monomer and emulsifying agent, and shell lotion is by shell
Monomer, cross-linking monomer and emulsifying agent composition；
(2) pre-emulsification of core lotion and shell lotion：The core lotion and shell lotion prepared in step (1) are stirred into progress respectively
Pre-emulsification, obtains core pre-emulsion after standing and shell pre-emulsion is spare respectively；
(3) synthesis of seed emulsion styrene core：Choose NaHCO3Buffer solution, water, emulsifying agent and part core pre-emulsion,
After quick stirring, oil bath heating, while stirring at low speed, added when being warming up to 65~70 DEG C and account for initiator gross mass 30~60%
Initiator bottoming, is continuously heating to 70~80 DEG C of 20~30min of reaction, to reactant blueing light, the reaction was continued 10~20min,
Then residual nucleus pre-emulsion being added dropwise and accounts for the initiator of initiator gross mass 10~30%, time for adding is controlled in 1~1.5h, after
10~20min of continuous reaction, is made seed emulsion styrene core；
(4) hud polymerization：The shell pre-emulsion in step (1) is added in seed emulsion styrene core made from step (3)
Initiator with initiator gross mass 10~30% is accounted for, controls and is added dropwise in 0.5~1h, after the reaction was continued 10~20min,
Obtain core-shell emulsion；
(5) strengthen：Remaining initiator is added dropwise in core-shell emulsion prepared by step (4), is warming up to 75~90 DEG C, reaction
1~2h, adjusts pH value to neutrality, products therefrom is the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter.
In the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of the particle diameter：
The proportion by weight of nuclear monomer and shell monomer is preferably 4 described in step (1):1, the cross-linking monomer is preferably
AMA, its dosage are preferably the 0.5~1.5% of nuclear monomer and shell monomer gross mass, and the emulsifying agent is preferably DNS-458, it is used
Amount is preferably the 2~5% of nuclear monomer and shell monomer gross mass；In its center lotion, the dosage of cross-linking monomer is preferably to be crosslinked list
The 78~82% of body gross mass, the dosage of emulsifying agent are preferably the 65~70% of emulsifying agent gross mass, in shell lotion, cross-linking monomer
Dosage be preferably the 18~22% of cross-linking monomer gross mass, the dosage of emulsifying agent be preferably emulsifying agent gross mass 20~
22%.
In the present invention, nuclear monomer only has styrene, and shell monomer can be only 4- vinylbenzaldehydes, or benzene
The mix monomer of ethene and 4- vinylbenzaldehydes；Wherein shell monomer is styrene and the mix monomer of 4- vinylbenzaldehydes
When, the dosage of styrene is 0.01~8 times of 4- vinylbenzaldehyde gross masses.
It is common to have DNS-86, DNS-268 and DNS-458 in amphoteric emulsifier, but present inventor is through overtesting
It was found that when being polymerize using the above two, thus obtained microsphere is unstable, easily aggregation, this is probably caused by emulsification is not thorough.And use
Then be not in that microballoon is unstable when DNS-458 polymerize, situation about easily assembling, polymerization situation is preferable, in consideration of it, the present invention adopts
Emulsifying agent is used as by the use of selection DNS-458.
To stablize micro-sphere structure, compact, be preferably added cross-linking monomer, common cross-linking monomer has divinylbenzene
(DVB) and AMA, but present inventor has found that DVB thus obtained microspheres are unstable by preliminary experiment, and AMA thus obtained microspheres are more steady
It is fixed, so, AMA is selected as cross-linking monomer.
Inertia is presented inside polymer microballoon, active functional group is contained in outside, and the surface for being supported on sphere carries out, not only
Efficiency, cost-effective can be improved, and is conducive to the stabilization of microballoon.Present inventor is found by experiment that, styrene
(St) with 4- vinylbenzaldehydes (VBA, Wulff G, Akelah A.Makromol Chem 1979,179:2647~2651)
Skeleton structure it is similar, compatibility is preferable, and polymerize after styrene it is inert.In consideration of it, present inventor selects styrene
St is as nuclear monomer, and VBA or 4- vinylbenzaldehyde VBA and styrene St are as shell monomer for 4- vinylbenzaldehydes；And work as core
The proportion by weight of monomer and shell monomer is 4:When 1, effect is preferable.
Rotating speed in step (2) during stirring is preferably 500~600rmp, and mixing time is preferably 10~20min；During standing
Between be preferably 10~20min.
The core pre-emulsion and shell pre-emulsion obtained after pre-emulsification is in off-white color, without lamination after standing.Pre-emulsified work
With mainly emulsifying agent constantly added in reaction system so that emulsifier concentration is no more than CMC (critical micells in system
Concentration), and achieve the purpose that not generate new core, and then be conducive to control the particle diameter of latex particle.
The dosage of pyrene pre-emulsion preferably accounts for 15~20%, NaHCO of total core pre-emulsion in the middle part of step (3)3Buffer solution
Dosage be preferably the 0~1% of nuclear monomer and shell monomer gross mass, the dosage of water is preferably 1~2 times of part core pre-emulsion,
The emulsifying agent is preferably DNS-458, its dosage is preferably the 8~13% of emulsifying agent gross mass.
It should be strongly noted that the particle diameter of microballoon passes through NaHCO3The concentration of buffer solution is regulated and controled, significant effect.
NaHCO3It is weak acid strong alkali salt, its aqueous solution just directly has certain buffer capacity, when its concentration is higher, gained latex particle
Particle diameter become larger.
Rotating speed in step (3) during quick stirring is 600~700rpm, and mixing time is 2~4min, and when oil bath heating is low
The rotating speed of speed stirring is 100~400rpm.
Specifically, when addition accounts for the initiator bottoming of initiator gross mass 30~60%, mixing speed is not
Can be too big, otherwise, microballoon uniformity can be deteriorated, and mixing speed is preferably in 100~400rpm.
Initiator described in step (3)~step (5) is ammonium persulfate, because whole reaction system be in water phase into
OK, compared to other persulfuric acid salts, ammonium persulfate solubility is big, and velocity of initiation is fast.Its dosage is preferably nuclear monomer and shell list
The 1~2% of body gross mass, step (5) is middle to adjust pH to neutrality, no styrene taste using ammonium hydroxide.
Using the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter made of the method for the present invention, use
The volume average particle size that Mastersizer particle size analyzers measure particle is 100~305nm, scattered uniformity is 0.1~
0.202.Its pattern is further looked at by transmission electron microscope, the results show is uniform spheroidal, and monodispersity is good, surface light
It is sliding, do not cohere, size is nanoscale, uniform particle diameter, and the size of its particle diameter can pass through NaHCO3The additive amount of solution carries out
Adjust, and increasing with VBA contents, core shell structure is obvious；Gel permeation chromatography (GPC) is the results show that peak type is after copolymerization
Typical Gaussian Profile, to be unimodal, showing styrene, there occurs effective copolymerization with 4- vinylbenzaldehydes；Ir data is shown
Show, in 2782~2886cm-1There is double-absorption peak, in 1710cm-1There is single absworption peak, it was demonstrated that the presence of aldehyde radical.
3rd technical problem to be solved by this invention is achieved through the following technical solutions：One kind is received containing aldehyde radical
Meter Wei Qiu-streptococcus lactis conjugate, using above-mentioned particle diameter adjustable nanoparticle containing aldehyde radical and lactic acid with core shell structure
Streptococcus is made.
The preparation method of the nanoparticle containing aldehyde radical-streptococcus lactis conjugate preferably includes following steps：Choose above-mentioned
The adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter, after being mixed with streptococcus lactis solution, vibration, centrifugation, take
Layer clear liquid, nanoparticle containing aldehyde radical-streptococcus lactis conjugate is made after dry.
Wherein vibrating and preferably vibrated using shaking table, hunting speed is preferably 70~110rpm, and duration of oscillation is preferably 10~
30h。
It is dry preferably to use freeze-drying.
Supernatant liquor, ultraviolet survey absorbance are taken, and then calculates its load capacity, and removes unreacted streptococcus lactis
NISIN, in triplicate, freeze drier drying, obtains nanoparticle containing aldehyde radical-streptococcus lactis conjugate, the results showed that load
Rate is about 95%, and the particle diameter of particle size analyzer measure gained conjugate is about 150~350nm, and dispersion degree is about 0.156~
0.289, transmission electron microscope shows that conjugate structure spherical in shape, size are homogeneous (transmission electron microscope picture is as shown in Figure 4), the size of its particle diameter
NaHCO in the preparation process of nanoparticle containing aldehyde radical can be passed through3The additive amount of solution is adjusted.
The present invention has the advantages that：
(1) nuclear monomer styrene (St) is similar to the skeleton structure of shell monomer 4- vinylbenzaldehydes (VBA), compatibility compared with
It is good, and styrene is inert after polymerization, styrene St is as nuclear monomer, 4- vinylbenzaldehyde VBA or 4- second for present invention selection
Alkenyl benzaldehyde VBA and styrene St is as shell monomer, and the manufactured nanoparticle containing aldehyde radical with core shell structure, this contains aldehyde radical
Nanoparticle particle size is adjustable, good dispersion degree；
(2) present invention, using DNS-458 as emulsifying agent, is made in the preparation process of the nanoparticle containing aldehyde radical using AMA
For cross-linking monomer, thus obtained microsphere is stablized, it is not easy to assembles.
(3) particle diameter of the nanoparticle of the invention containing aldehyde radical is in preparation process, by adding NaHCO3Buffer solution it is dense
Spend and the particle diameter of the nanoparticle containing aldehyde radical is regulated and controled, significant effect；
(4) selected materials of the present invention it is simple and easy to get, prepare the method therefor of nanoparticle containing aldehyde radical be industrialize it is extensive
The emulsion polymerization technology used, is easier to realize industrialized production；
(5) aldehyde radical of the nanoparticle of the invention containing aldehyde radical is coupled with the amino in streptococcus lactis Nisin by Schiff,
Streptococcus lactis conjugate is obtained, not only can strengthen stability, Er Qiezuo to avoid the high temperature deactivation of streptococcus lactis Nisin
It is added to for a kind of functional component in packaging film, the compatibility with packaging film can also be strengthened, has in active antibacterial packaging film
There is good application prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the nanoparticle containing aldehyde radical prepared in embodiment 1, styrene and 4- wherein in shell monomer
The relationship between quality of vinylbenzaldehyde is 0：4g；
Fig. 2 is the gel permeation chromatography (GPC) of the nanoparticle containing aldehyde radical prepared in embodiment 1, and wherein A represents purified petroleum benzin second
Alkene, B represent styrene and the emulsion copolymers of 4- vinylbenzaldehydes, and operation condition is identical；
Fig. 3 is the nanoparticle containing aldehyde radical and nanoparticle containing aldehyde radical-streptococcus lactis conjugate prepared in embodiment 1
Infrared spectrogram, wherein, A is pure styrene；B represents styrene and the emulsion copolymers of 4- vinylbenzaldehydes, both
Operation condition is identical；C is after B loads Nisin；
Fig. 4 is the transmission electron microscope picture of nanoparticle containing the aldehyde radical-streptococcus lactis conjugate prepared in embodiment 4.
Embodiment
The present invention is described in further detail for the embodiment provided below in conjunction with inventor, each group used below
Point, such as indicated without special, be commercially available.
Embodiment 1
The adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter provided in this embodiment, this contains aldehyde radical nanoparticle
Particle diameter be 173nm, dispersion degree 0.2, the nuclear monomer of the nanoparticle containing aldehyde radical is styrene, and shell monomer is 4- vinyl benzene first
The proportion by weight of aldehyde VBA, wherein nuclear monomer and shell monomer are 4:1.
The preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of the particle diameter is as follows：
(1) screening and preparation of emulsifying agent and initiator
In amphoteric emulsifier, common have DNS-86, DNS-268 and DNS-458, but during using the above two polymerizations, institute
It is unstable to obtain microballoon, easily aggregation, this is probably caused by emulsification is not thorough, in consideration of it, selection DNS-458 (is bought in wide
State double bond trade Co., Ltd, herein be only enumerate, be not defined, other commercial product also can), its effect is good, gained
Microballoon is stablized, it is not easy to assembles, accounts for core, the 3.35% of shell monomer amount gross mass, accurately weigh 0.67gDNS-458 and be dissolved in 64mL
In deionized water, emulsifier solution is configured.
Selection ammonium persulfate (APS) is used as initiator, accounts for core, the 1.6% of shell monomer gross mass, it is molten to weigh 0.32g APS
In 12mL deionized waters, the APS solution of 12mL is configured to.
(2) pre-emulsification of core lotion and shell lotion
Inertia is presented inside polymer microballoon, active functional group is contained in outside, and the surface for being supported on sphere carries out, not only
Efficiency, cost-effective can be improved, and is conducive to the stabilization of microballoon.Styrene (St) and 4- vinylbenzaldehydes VBA (VBA,
Wulff G,Akelah A.Makromol Chem 1979,179:2647~2651) skeleton structure is similar, and compatibility is preferable,
And styrene is inert after polymerizeing.In consideration of it, selection St is nuclear monomer, VBA is shell monomer, and the proportion by weight of the two is 4：1.
To stablize micro-sphere structure, compact, add cross-linking monomer, common cross-linking monomer have divinylbenzene (DVB) and
AMA (one horse reagent Co., Ltd of Guangzhou, purity：99%, it is only to enumerate herein, is not defined, other commercial product
Can), but find that DVB thus obtained microspheres are unstable by preliminary experiment, and use AMA thus obtained microspheres to stablize, so, select AMA conducts
Cross-linking monomer, accounts for the 1% of nuclear monomer styrene and shell monomer 4- vinylbenzaldehyde gross masses.
Therefore, the composition of core lotion is St 16g, AMA 0.16g, DNS-458 44mL；The composition of shell lotion is VBA
4g、AMA 0.04g、DNS-458 14mL.Respectively by the core lotion configured and shell lotion in 250mL conical flasks, machinery stirs
Mix (rotating speed 570rmp) and carry out pre-emulsification, about 15min, lotion is in off-white color, without lamination after standing 15min.
(3) synthesis of seed emulsion styrene core
0.01gNaHCO is added in 250mL reaction bulbs3Buffer solution, 10mL water, 6mLDNS-458 solution and 10mL cores
Pre-emulsion, and (rotating speed is 600~700rmp) 3min is quickly stirred, then oil bath heating, mechanical agitation speed will be 285rmp；
5mL APS are added when being warming up to 70 DEG C, then heat to 78 DEG C, react about 20~30min, reactant blueing light, continues anti-
10min is answered, core pre-emulsion, the 3mL APS solution of residue 46mL is then added dropwise, controls and is added dropwise in 1~1.5h；The reaction was continued
10min, specifically, mixing speed can not be too big, and otherwise, microballoon uniformity is deteriorated, second, the particle diameter of microballoon passes through
NaHCO3The concentration of buffer solution is regulated and controled, significant effect.
(4) emulsion polymerization of VBA shells
In above-mentioned 78 DEG C of reaction system, the 16mL shells pre-emulsion, the 2mL APS solution that are prepared in a dropping step (2), control
System is added dropwise in 0.5~1h, and after the reaction was continued 10min, remaining 2mLAPS solution is added dropwise, and is warming up to 85 DEG C, reacts 1h,
PH value is adjusted to neutrality, no styrene taste with ammonium hydroxide.
The particle diameter of particle size determination instrument measure gained latex ion is 173nm, dispersion degree 0.2, by transmission electron microscope into one
Step observes its pattern (Fig. 1), and the results show size is homogeneous, the clear and definite nanoparticle structure of structure, and the size of its particle diameter can lead to
Cross NaHCO3The additive amount of solution is adjusted；Molecular weight hoists after gel permeation chromatography (GPC) data show (Fig. 2) copolymerization
Mobile, the number-average molecular weight Mn of pure styrene is 111549, and monodispersity PDI is 1.5, and Mn is for 165655, PDI after being copolymerized
1.35, and be typical Gaussian Profile, to be unimodal, showing styrene, there occurs effective copolymerization with 4- vinylbenzaldehydes；It is red
External spectrum data show (B in Fig. 3), and copolymer is in 2782-2886cm-1There is double-absorption peak, in 1710cm-1There is single absworption peak,
Prove the presence of aldehyde radical.
Embodiment 2
The adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter provided in this embodiment, this contains aldehyde radical nanoparticle
Particle diameter be about 300nm, dispersion degree 0.202, the nuclear monomer of the nanoparticle containing aldehyde radical is styrene, and shell monomer is 4- vinyl
Benzaldehyde VBA and styrene St, the wherein proportion by weight of nuclear monomer and shell monomer are 4:1,4- vinyl benzene first in shell monomer
The proportion by weight of aldehyde VBA and styrene St are 1:6.
The preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of the particle diameter is as different from Example 1：
The dosage of cross-linking monomer is the 0.5% of nuclear monomer and shell monomer gross mass.
The dosage of emulsifying agent is the 5% of nuclear monomer and shell monomer gross mass, and in its center lotion, the dosage of cross-linking monomer is
The 82% of cross-linking monomer gross mass, the dosage of emulsifying agent are the 70% of emulsifying agent gross mass, in shell lotion, the dosage of cross-linking monomer
For the 18% of cross-linking monomer gross mass, the dosage of emulsifying agent is the 20% of emulsifying agent gross mass.
Initiator is ammonium persulfate, its dosage is the 1% of nuclear monomer and shell monomer gross mass.
During the pre-emulsification of core lotion and shell lotion, rotating speed during stirring is 500rmp, mixing time 20min, during standing
Between be 20min.
During the synthesis of seed emulsion styrene core, the dosage of part core pre-emulsion accounts for 15%, NaHCO of total core pre-emulsion3
The dosage of buffer solution is the 0.5% of nuclear monomer styrene and shell monomer 4- vinylbenzaldehyde gross masses, and the dosage of water is portion
2 times of pyrene pre-emulsion, emulsifying agent DNS-458, its dosage are the 10% of emulsifying agent gross mass.
During the synthesis of seed emulsion styrene core, rotating speed during quick stirring is 600rpm, mixing time 4min, oil bath
The rotating speed of stirring at low speed is 100rpm during heating, and reaction temperature is 65 DEG C during bottoming, and initiator amount accounts for initiator gross mass
60%, 70 DEG C of reaction 30min are continuously heating to, to reactant blueing light, then the pre- breast of residual nucleus is added dropwise in the reaction was continued 20min
Liquid and the initiator for accounting for initiator gross mass 10%, time for adding control is in 1~1.5h, the reaction was continued 10~20min, obtained kind
Sub- emulsion styrene core.
During hud polymerization, the dosage of initiator accounts for the 10% of initiator gross mass, controls and is added dropwise in 0.5~1h,
The reaction was continued 10min.
During reinforcing, 75 DEG C are warming up to, reacts 2h, initiator amount accounts for initiator gross mass 20%.
Embodiment 3
The adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter provided in this embodiment, this contains aldehyde radical nanoparticle
Particle diameter be about 120nm, dispersion degree 0.15, the nuclear monomer of the nanoparticle containing aldehyde radical is styrene, and shell monomer is 4- vinyl
Benzaldehyde VBA and styrene St, the wherein proportion by weight of nuclear monomer and shell monomer are 4:1,4- vinyl benzene first in shell monomer
The proportion by weight of aldehyde VBA and styrene St are 1:8.
The preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of the particle diameter is as different from Example 1：
The dosage of cross-linking monomer is the 1.5% of nuclear monomer and shell monomer gross mass.
The dosage of emulsifying agent is the 3% of nuclear monomer and shell monomer gross mass；In its center lotion, the dosage of cross-linking monomer is
The 78% of cross-linking monomer gross mass, the dosage of emulsifying agent are the 65% of emulsifying agent gross mass, in shell lotion, the dosage of cross-linking monomer
For the 22% of cross-linking monomer gross mass, the dosage of emulsifying agent is the 22% of emulsifying agent gross mass.
Initiator is ammonium persulfate, its dosage is the 2% of nuclear monomer and shell monomer gross mass.
During the pre-emulsification of core lotion and shell lotion, rotating speed during stirring is 600rmp, mixing time 10min, time of repose
For 10min.
During the synthesis of seed emulsion styrene core, the dosage of part core pre-emulsion accounts for the 20% of total core pre-emulsion, no added
NaHCO3Buffer solution, the dosage of water are 1.5 times, emulsifying agent DNS-458 of part core pre-emulsion, its dosage is total for emulsifying agent
The 13% of quality.
During the synthesis of seed emulsion styrene core, rotating speed during quick stirring is 700rpm, mixing time 2min, oil bath
The rotating speed of stirring at low speed is 400rpm during heating, and reaction temperature is 70 DEG C during bottoming, and initiator amount accounts for initiator gross mass
30%, 80 DEG C of reaction 20min are continuously heating to, to reactant blueing light, then the pre- breast of residual nucleus is added dropwise in the reaction was continued 10min
Liquid and the initiator for accounting for initiator gross mass 30%, time for adding control is in 1~1.5h, the reaction was continued 10~20min, obtained kind
Sub- emulsion styrene core.
During hud polymerization, the dosage of initiator accounts for the 30% of initiator gross mass, controls and is added dropwise in 0.5~1h,
The reaction was continued 10min.
During reinforcing, 90 DEG C are warming up to, reacts 1h, initiator amount accounts for initiator gross mass 10%.
Embodiment 4
Nanoparticle containing aldehyde radical provided in this embodiment-streptococcus lactis conjugate, using the particle diameter prepared in embodiment 1
The adjustable nanoparticle containing aldehyde radical with core shell structure is made with streptococcus lactis.
Specifically preparation process is：60mL lotion microballoons prepared by Example 1, the streptococcus lactis with 80mL10mg/mL
Solution mixing, the speed concussion 24h of 100rpm, ultracentrifugation, takes supernatant liquor, ultraviolet survey absorbance, and then it is negative to calculate it
Carrying capacity, and unreacted streptococcus lactis is removed, in triplicate, freeze drier drying, obtains nanoparticle containing aldehyde radical-lactic acid chain
Coccus conjugate (alternatively referred to as 4- vinylbenzaldehydes-streptococcus lactis), load factor 95%, particle size analyzer measure institute
The particle diameter for obtaining conjugate is 256nm, and dispersion degree 0.2, transmission electron microscope (see Fig. 4) display conjugate structure spherical in shape, size are equal
One, the size of its particle diameter can pass through NaHCO in the preparation process of nanoparticle containing aldehyde radical3The additive amount of solution is adjusted；It is red
External spectrum (see C in Fig. 3) data are shown in 1730cm-1The characteristic peak of neighbouring aldehyde weakens, and corresponding in 3063cm-1Place occurs
The characteristic absorption peak of imines, in addition, 1614-1620cm-1Go out to have stretching vibration peak in the range of, it was demonstrated that the depositing of Schiff
.Manufactured nanoparticle containing aldehyde radical-streptococcus lactis conjugate can be added in packaging film as a kind of functional component, also
The compatibility with packaging film can be strengthened, had a good application prospect in active antibacterial packaging film.
Embodiment 5
Nanoparticle containing aldehyde radical provided in this embodiment-streptococcus lactis conjugate, using the particle diameter prepared in embodiment 2
The adjustable nanoparticle containing aldehyde radical with core shell structure is made with streptococcus lactis.
Specifically preparation process is：60mL lotion microballoons prepared by Example 2, the streptococcus lactis with 40mL10mg/mL
Solution mixing, 90rpm speed concussion 30h, ultracentrifugation, takes supernatant liquor, ultraviolet survey absorbance, and then calculates its load
Amount, and unreacted streptococcus lactis is removed, in triplicate, freeze drier drying, obtains copolymer nanometer microsphere containing aldehyde radical-breast
Acid streptococci conjugate.
Embodiment 6
Nanoparticle containing aldehyde radical provided in this embodiment-streptococcus lactis conjugate, using the particle diameter prepared in embodiment 3
The adjustable nanoparticle containing aldehyde radical with core shell structure is made with streptococcus lactis.
Specifically preparation process is：60mL lotion microballoons prepared by Example 2, the streptococcus lactis with 20mL10mg/mL
Solution mixing, the speed concussion 10h of 110rpm, ultracentrifugation, takes supernatant liquor, ultraviolet survey absorbance, and then it is negative to calculate it
Carrying capacity, and unreacted streptococcus lactis is removed, in triplicate, freeze drier drying, obtains aldehyde radical copolymer nanometer microsphere-breast
Acid streptococci conjugate.
The aldehyde radical of the nanoparticle of the invention containing aldehyde radical is coupled with the amino in streptococcus lactis Nisin by Schiff, is obtained
Streptococcus lactis conjugate is obtained, not only can strengthen stability, and conduct to avoid the high temperature deactivation of streptococcus lactis Nisin
A kind of functional component is added in packaging film, can also strengthen the compatibility with packaging film, has in active antibacterial packaging film
Good application prospect.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included in protection scope of the present invention.
Claims (10)
1. a kind of adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter, it is characterized in that：The nanoparticle containing aldehyde radical
Particle diameter is 100 ~ 305 nm, and dispersion degree is 0.1 ~ 0.202, and the nuclear monomer of the nanoparticle containing aldehyde radical is styrene, shell monomer
For 4- vinylbenzaldehydes, or shell monomer is styrene and the mix monomer of 4- vinylbenzaldehydes, the nuclear monomer and described
The proportion by weight of both shell monomers is 4:1；
The preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of the particle diameter, comprises the following steps：
（1）Prepare core lotion and shell lotion：Core lotion is made of nuclear monomer, cross-linking monomer and emulsifying agent, shell lotion by shell monomer,
Cross-linking monomer and emulsifying agent composition；
（2）The pre-emulsification of core lotion and shell lotion：By step（1）The core lotion and shell lotion of middle preparation stir respectively carries out pre- breast
Change, obtain core pre-emulsion respectively after standing and shell pre-emulsion is spare；
（3）The synthesis of seed emulsion styrene core：Choose NaHCO3Buffer solution, water, emulsifying agent and part core pre-emulsion, quickly
After stirring, oil bath heating, while stirring at low speed, the initiator for accounting for initiator gross mass 30 ~ 60% is added when being warming up to 65 ~ 70 DEG C
Bottoming, is continuously heating to 70 ~ 80 DEG C of 20 ~ 30min of reaction, and to reactant blueing light, then the reaction was continued 10 ~ 20min is added dropwise surplus
Cokernel pre-emulsion and the initiator for accounting for initiator gross mass 10 ~ 30%, time for adding control in 1 ~ 1.5h, the reaction was continued 10 ~
20min, is made seed emulsion styrene core；
（4）Hud polymerization：In step（3）Step is added in obtained seed emulsion styrene core（1）In shell lotion and accounting for draw
The initiator of agent gross mass 10 ~ 30% is sent out, controls and is added dropwise in 0.5 ~ 1h, after the reaction was continued 10 ~ 20min, obtains nucleocapsid breast
Liquid；
（5）Strengthen：In step（4）Remaining initiator is added dropwise in the core-shell emulsion of preparation, is warming up to 75 ~ 90 DEG C, reacts 1 ~ 2h,
PH value is adjusted to neutrality, products therefrom is the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter；
Step（3）Described in NaHCO3The dosage of buffer solution is the 0 ~ 1% of nuclear monomer and shell monomer gross mass.
2. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter described in claim 1, its feature
It is to comprise the following steps：
（1）Prepare core lotion and shell lotion：Core lotion is made of nuclear monomer, cross-linking monomer and emulsifying agent, shell lotion by shell monomer,
Cross-linking monomer and emulsifying agent composition；
（2）The pre-emulsification of core lotion and shell lotion：By step（1）The core lotion and shell lotion of middle preparation stir respectively carries out pre- breast
Change, obtain core pre-emulsion respectively after standing and shell pre-emulsion is spare；
（3）The synthesis of seed emulsion styrene core：Choose NaHCO3Buffer solution, water, emulsifying agent and part core pre-emulsion, quickly
After stirring, oil bath heating, while stirring at low speed, the initiator for accounting for initiator gross mass 30 ~ 60% is added when being warming up to 65 ~ 70 DEG C
Bottoming, is continuously heating to 70 ~ 80 DEG C of 20 ~ 30min of reaction, and to reactant blueing light, then the reaction was continued 10 ~ 20min is added dropwise surplus
Cokernel pre-emulsion and the initiator for accounting for initiator gross mass 10 ~ 30%, time for adding control in 1 ~ 1.5h, the reaction was continued 10 ~
20min, is made seed emulsion styrene core；
（4）Hud polymerization：In step（3）Step is added in obtained seed emulsion styrene core（1）In shell lotion and accounting for draw
The initiator of agent gross mass 10 ~ 30% is sent out, controls and is added dropwise in 0.5 ~ 1h, after the reaction was continued 10 ~ 20min, obtains nucleocapsid breast
Liquid；
（5）Strengthen：In step（4）Remaining initiator is added dropwise in the core-shell emulsion of preparation, is warming up to 75 ~ 90 DEG C, reacts 1 ~ 2h,
PH value is adjusted to neutrality, products therefrom is the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter.
3. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter according to claim 2, its
It is characterized in：Step（1）Described in the proportion by weight of nuclear monomer and shell monomer be 4:1, the cross-linking monomer is AMA, its dosage
For the 0.5 ~ 1.5% of nuclear monomer and shell monomer gross mass, the emulsifying agent is DNS-458, its dosage is total for nuclear monomer and shell monomer
The 2 ~ 5% of quality；In its center lotion, the dosage of cross-linking monomer is the 78 ~ 82% of cross-linking monomer gross mass, and the dosage of emulsifying agent is
The 65 ~ 70% of emulsifying agent gross mass, in shell lotion, the dosage of cross-linking monomer is the 18 ~ 22% of cross-linking monomer gross mass, emulsifying agent
Dosage is the 20 ~ 22% of emulsifying agent gross mass.
4. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter according to claim 2, its
It is characterized in：Step（2）Rotating speed during middle stirring is 500 ~ 600rpm, and mixing time is 10 ~ 20min；Time of repose for 10 ~
20min。
5. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter according to claim 2, its
It is characterized in：Step（3）The dosage of middle part pyrene pre-emulsion accounts for the 15 ~ 20% of total core pre-emulsion, and the dosage of water is part core pre-emulsion
1 ~ 2 times, the emulsifying agent is DNS-458, its dosage is the 8 ~ 13% of emulsifying agent gross mass.
6. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter according to claim 2, its
It is characterized in：Step（3）In quick stirring when rotating speed be 600 ~ 700rpm, mixing time is 2 ~ 4min, low speed during oil bath heating
The rotating speed of stirring is 100 ~ 400rpm.
7. the preparation method of the adjustable nanoparticle containing aldehyde radical with core shell structure of particle diameter according to claim 2, its
It is characterized in：Step（3）~ step（5）Described in initiator be ammonium persulfate, its dosage is nuclear monomer and shell monomer gross mass
1 ~ 2%, step（5）It is middle that pH is adjusted to neutrality, no styrene taste using ammonium hydroxide.
8. a kind of nanoparticle containing aldehyde radical-streptococcus lactis conjugate, it is characterized in that：Can using the particle diameter described in claim 1
The manufactured nanometer containing aldehyde radical of any one of the nanoparticle containing aldehyde radical with core shell structure or claim 2-7 adjusted preparation method is micro-
Ball is made with streptococcus lactis.
9. the preparation method of nanoparticle containing aldehyde radical-streptococcus lactis conjugate described in claim 8, it is characterized in that including with
Lower step：The particle diameter in claim 1 adjustable nanoparticle containing aldehyde radical or claim 2-7 with core shell structure is chosen to appoint
Nanoparticle containing aldehyde radical made of one preparation method, after being mixed with streptococcus lactis solution, vibration, centrifugation, take supernatant liquor,
Nanoparticle containing aldehyde radical-streptococcus lactis conjugate is made after drying.
10. the preparation method of nanoparticle containing aldehyde radical according to claim 9-streptococcus lactis conjugate, it is characterized in that：
Vibration is vibrated using shaking table, and hunting speed is 70 ~ 110rpm, and duration of oscillation is 10 ~ 30h.
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| CN102590506A (en) * | 2012-02-16 | 2012-07-18 | 上海师范大学 | Method for rapidly detecting and screening staphylococcus aureus |
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| CN102786609A (en) * | 2012-07-17 | 2012-11-21 | 中北大学 | Macromolecule immobilized cationic porphyrin compound and its preparation method |
| CN104624170A (en) * | 2014-12-25 | 2015-05-20 | 佛山市博新生物科技有限公司 | Adsorbent for treating gram bacterial infection and blood perfusion device |
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