CN105968245A - 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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- CN105968245A CN105968245A CN201610331149.7A CN201610331149A CN105968245A CN 105968245 A CN105968245 A CN 105968245A CN 201610331149 A CN201610331149 A CN 201610331149A CN 105968245 A CN105968245 A CN 105968245A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 84
- 239000002245 particle Substances 0.000 title claims abstract description 60
- 239000011258 core-shell material Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 43
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 124
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 75
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical group C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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 21
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims description 87
- 239000003995 emulsifying agent Substances 0.000 claims description 41
- 239000003999 initiator Substances 0.000 claims description 38
- 238000004132 cross linking Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 241000194017 Streptococcus Species 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005728 strengthening Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000001804 emulsifying effect 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
- 238000000034 method Methods 0.000 claims description 3
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 241000194035 Lactococcus lactis Species 0.000 abstract 4
- 235000014897 Streptococcus lactis Nutrition 0.000 abstract 4
- 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
- 229920006280 packaging film Polymers 0.000 description 8
- 239000012785 packaging film Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 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
- 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 6
- 108010053775 Nisin Proteins 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000004309 nisin Substances 0.000 description 6
- 235000010297 nisin Nutrition 0.000 description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 5
- DHEJIZSVHGOKMJ-UHFFFAOYSA-N 2-ethenylbenzaldehyde Chemical compound C=CC1=CC=CC=C1C=O DHEJIZSVHGOKMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241001478240 Coccus Species 0.000 description 3
- 240000000203 Salix gracilistyla Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009432 framing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000005199 ultracentrifugation Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010023644 Lacrimation increased Diseases 0.000 description 1
- 239000002253 acid Substances 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
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 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
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 239000000693 micelle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 persulfuric acid salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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, be specifically related to that a kind of particle diameter is adjustable has receiving containing aldehyde radical of nucleocapsid structure
Meter Wei Qiu and preparation method thereof.
Background technology
The functional polymer containing aldehyde radical have general, flexible, facilitate the advantages such as use, the most noticeable.At present containing aldehyde radical
Monomer mainly has three kinds: acrylic aldehyde, 4-vinylbenzaldehyde (VBA) and various substituted 4-vinyl bigcatkin willow aldehydes (IVDG).
Wherein, wherein acrylic aldehyde as monomer obtain polymer microballoon be most common be also most, but monomer toxicity is big, explosive,
Lacrimation is strong, limits it and applies further.2007, wool professor and professor Lu Jiang reported 4-vinylbenzaldehyde respectively
(Macromolecules, 2007,40:793～795) and ferrocene substituted 4-vinyl bigcatkin willow aldehydes
(Macromolecules, 2007,40:1891～1896), and be polymerized by RAFT, obtain clear and definite the containing of structure
Aldehyde radical polymer, compare the 4-vinyl bigcatkin willow aldehydes with substituent group, and the synthesis step of VBA monomer is simple, and productivity is more
Height, therefore, in recent years, the research of VBA base polymer receives much concern, but obtains the regulatable 4-of particle diameter by emulsion polymerization
Vinylbenzaldehyde polymer nano-microspheres has no that it is reported.
After bioactive molecule and functional polymer are puted together, can effectively improve its dissolubility, stability, activity and add
Work performance, can also strengthen the performances such as its compatibility sometimes.The most in recent years Polymer-bioactive molecular conjugate medicine,
Biotechnology and nano science field cause and pay close attention to widely.Streptococcus acidi lactici (Ninsin) can be by the enzyme in human body
Degraded, digestion, be a kind of efficient, safe and nontoxic, antiseptics for natural food of having no side effect.But there is presently no by
Particle diameter regulatable 4-vinylbenzaldehyde polymer nano-microspheres puts together grinding of aspect mutually with streptococcus acidi lactici (Ninsin)
Study carefully.
Summary of the invention
To be solved by this invention first technical problem is how to provide a kind of particle diameter adjustable have nucleocapsid structure containing aldehyde
Based nanospheres, it is adjustable that this contains aldehyde radical Nano microsphere size, good dispersion degree.
Second technical problem to be solved by this invention be to provide above-mentioned particle diameter adjustable have nucleocapsid structure containing aldehyde radical
The preparation method of Nano microsphere.
3rd technical problem to be solved by this invention is to provide a kind of containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate
And preparation method thereof, this contains aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate by by containing the aldehyde radical in aldehyde radical Nano microsphere
Amino phase coupling with streptococcus acidi lactici, is avoided that the high temperature deactivation of streptococcus acidi lactici, 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
Have nucleocapsid structure containing aldehyde radical Nano microsphere, this particle diameter containing aldehyde radical Nano microsphere is 100～305nm, and dispersion is
0.1～0.202, the described nuclear monomer containing aldehyde radical Nano microsphere is styrene, and shell monomer is 4-vinylbenzaldehyde, or shell list
Body is styrene and the mix monomer of 4-vinylbenzaldehyde, described nuclear monomer and the proportion by weight of described both shell monomers
For 4:1.
Second technical problem to be solved by this invention is achieved through the following technical solutions: above-mentioned particle diameter is adjustable
There is the preferred preparation method of the one of which containing aldehyde radical Nano microsphere of nucleocapsid structure, comprise the following steps:
(1) preparation core emulsion and shell emulsion: core emulsion is made up of nuclear monomer, cross-linking monomer and emulsifying agent, shell emulsion by
Shell monomer, cross-linking monomer and emulsifying agent composition；
(2) core emulsion and the pre-emulsification of shell emulsion: the core emulsion of preparation in step (1) and shell emulsion are stirred respectively into
Row pre-emulsification, obtains core pre-emulsion respectively after standing and shell pre-emulsion is standby；
(3) synthesis of seed emulsion styrene core: choose NaHCO3Buffer solution, water, emulsifying agent and part core are pre-
Emulsion, quickly after stirring, oil bath is heated, stirring at low speed simultaneously, adds and account for initiator gross mass when being warming up to 65～70 DEG C
30～the initiator bottoming of 60%, it is continuously heating to 70～80 DEG C of reactions 20～30min, to reactant blueing light, continues anti-
Answer 10～20min, then drip residual nucleus pre-emulsion and account for initiator gross mass 10～the initiator of 30%, time for adding control
System, 1～1.5h, continues reaction 10～20min, prepares seed emulsion styrene core；
(4) hud polymerization: add the shell in step (1) in the seed emulsion styrene core that step (3) prepares pre-
Emulsion and account for initiator gross mass 10～the initiator of 30%, controls to drip in 0.5～1h complete, continues reaction 10～20min
After, obtain core-shell emulsion；
(5) strengthening: drip remaining initiator in core-shell emulsion prepared by step (4), be warming up to 75～90 DEG C,
Reaction 1～2h, regulation pH value is to neutral, and it is micro-that products therefrom is the adjustable nanometer containing aldehyde radical with nucleocapsid structure of particle diameter
Ball.
In the adjustable preparation method containing aldehyde radical Nano microsphere with nucleocapsid structure of this particle diameter:
Nuclear monomer described in step (1) is preferably 4:1 with the proportion by weight of shell monomer, and described cross-linking monomer is preferably
AMA, its consumption is preferably nuclear monomer and the 0.5 of shell monomer gross mass～1.5%, and described emulsifying agent is preferably DNS-458,
Its consumption is preferably nuclear monomer and the 2 of shell monomer gross mass～5%；In its center emulsion, the consumption of cross-linking monomer is preferably
The 78～82% of cross-linking monomer gross mass, the consumption of emulsifying agent is preferably the 65～70% of emulsifying agent gross mass, in shell emulsion,
The consumption of cross-linking monomer is preferably the 18～22% of cross-linking monomer gross mass, and the consumption of emulsifying agent is preferably emulsifying agent gross mass
20～22%.
In the present invention, nuclear monomer only has styrene, and shell monomer can simply be 4-vinylbenzaldehyde, it is also possible to for benzene
Ethylene and the mix monomer of 4-vinylbenzaldehyde；Wherein shell monomer is styrene and the mix monomer of 4-vinylbenzaldehyde
Time, cinnamic consumption is 0.01～8 times of 4-vinylbenzaldehyde gross mass.
In amphoteric emulsifier, conventional has DNS-86, DNS-268 and DNS-458, but present inventor passes through
Test finds, when using the above two to be polymerized, thus obtained microsphere is unstable, easily assembles, and this is probably what emulsifying the most thoroughly caused.
And when using DNS-458 to be polymerized, then not havinging microsphere unstable, situation about easily assembling, polymerization situation is preferable, mirror
In this, the present invention uses selection DNS-458 as emulsifying agent.
For making micro-sphere structure stable, compacting, be preferably added cross-linking monomer, conventional cross-linking monomer has divinylbenzene (DVB)
And AMA, but by preliminary experiment, present inventor finds that DVB thus obtained microsphere is unstable, and AMA thus obtained microsphere ratio
More stable, so, select AMA as cross-linking monomer.
Presenting inertia inside polymer microballoon, outside containing active functional group, the surface being supported on spheroid is carried out, not only
Can improve efficiency, cost-effective, and beneficially the stablizing of microsphere.Present inventor is found by experiment that, benzene second
Alkene (St) and 4-vinylbenzaldehyde (VBA, Wulff G, Akelah A.Makromol Chem 1979,179:2647～
2651) framing structure is similar, and the compatibility is preferable, and after polymerization, styrene is inert.In consideration of it, present inventor
Select styrene St as nuclear monomer, 4-vinylbenzaldehyde VBA or 4-vinylbenzaldehyde VBA and styrene St
As shell monomer；And when the proportion by weight of nuclear monomer and shell monomer is 4:1, effect is preferable.
In step (2), rotating speed 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 the shell pre-emulsion that obtain after pre-emulsification are off-white color, without lamination after standing.Pre-emulsified effect
Mainly emulsifying agent is constantly added in reaction system so that in system, emulsifier concentration is (critical less than CMC
Micellar concentration), and reach not generate the purpose of new core, and then be conducive to controlling the particle diameter of latex particle.
The consumption of step (3) middle part pyrene pre-emulsion preferably comprises the 15～20% of total core pre-emulsion, NaHCO3Buffer solution
Consumption be preferably nuclear monomer and the 0 of shell monomer gross mass～1%, the consumption of water is preferably 1～2 times of part core pre-emulsion,
Described emulsifying agent is preferably DNS-458, and its consumption is preferably the 8～13% of emulsifying agent gross mass.
It should be strongly noted that the particle diameter of microsphere passes through NaHCO3The concentration of buffer solution regulates and controls, and effect is notable.
NaHCO3Being weak acid strong alkali salt, its aqueous solution the most directly has certain buffer capacity, when its concentration is higher, and gained breast
The particle diameter of micelle becomes big.
Rotating speed when quickly stirring in step (3) is 600～700rpm, and mixing time is 2～4min, low during oil bath heating
The rotating speed of speed stirring is 100～400rpm.
Specifically, add account for initiator gross mass 30～60% initiator bottoming time, mixing speed can not
Too big, otherwise, microsphere uniformity can be deteriorated, and mixing speed is preferably 100～400rpm.
Initiator described in step (3)～step (5) is Ammonium persulfate., because whole reaction system is to enter in aqueous phase
OK, compared to other persulfuric acid salts, Ammonium persulfate. dissolubility is big, and velocity of initiation is fast.Its consumption be preferably nuclear monomer and
The 1～2% of shell monomer gross mass, uses ammonia regulation pH the most neutral, without styrene taste in step (5).
Use the particle diameter made of the inventive method adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere, use
It is 100～305nm that Mastersizer particle size analyzer records the volume average particle size of granule, and scattered concordance is
0.1～0.202.Further looking at its pattern by transmission electron microscope, result is shown as uniform spheroidal, and monodispersity is good,
Smooth surface, does not cohere, a size of nanoscale, uniform particle diameter, and the size of its particle diameter can pass through NaHCO3Solution
Addition be adjusted, and increasing along with VBA content, nucleocapsid structure is obvious；Gel permeation chromatography (GPC)
Result shows, copolymerization postpeak type is typical Gauss distribution, for unimodal, shows that styrene occurs with 4-vinylbenzaldehyde
Effective copolymerization；Ir data shows, 2782～2886cm-1There is double-absorption peak, at 1710cm-1There is single suction
Receive peak, it was demonstrated that the existence of aldehyde radical.
3rd technical problem to be solved by this invention is achieved through the following technical solutions: a kind of nanometer in aldehyde radical
Microsphere-streptococcus acidi lactici conjugate, use above-mentioned particle diameter adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere and lactic acid
Streptococcus is made.
This preparation method containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate preferably includes following steps: choose above-mentioned grain
Footpath is adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere, after mixing with streptococcus acidi lactici solution, vibrate, centrifugal, take
The supernatant, the most i.e. prepares containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate.
Wherein vibration preferably employs shaking table vibration, and hunting speed is preferably 70～110rpm, and duration of oscillation is preferably 10～30h.
It is dried and preferably employs lyophilization.
Taking the supernatant, ultraviolet surveys absorbance, and then calculates its load capacity, and removes unreacted streptococcus acidi lactici NISIN,
In triplicate, freezer dryer is dried, and must contain aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate, and result shows load factor
Being about 95%, particle size analyzer measures the particle diameter of gained conjugate and is about 150～350nm, and dispersion is about 0.156～0.289,
Transmission electron microscope display conjugate structure spherical in shape, size homogeneous (transmission electron microscope picture is as shown in Figure 4), the size of its particle diameter
Can be by containing NaHCO in aldehyde radical Nano microsphere preparation process3The addition of solution is adjusted.
There is advantages that
(1) nuclear monomer styrene (St) is similar to the framing structure of shell monomer 4-vinylbenzaldehyde (VBA), phase
Capacitive is preferable, and after polymerization, styrene is inert, and the present invention selects styrene St as nuclear monomer, 4-vinylbenzaldehyde
VBA or 4-vinylbenzaldehyde VBA and styrene St as shell monomer, make have nucleocapsid structure containing aldehyde radical
Nano microsphere, it is adjustable that this contains aldehyde radical Nano microsphere size, good dispersion degree；
(2) present invention is in the preparation process containing aldehyde radical Nano microsphere, uses DNS-458 as emulsifying agent, uses
AMA is as cross-linking monomer, and thus obtained microsphere is stable, it is not easy to assemble.
(3) present invention particle diameter containing aldehyde radical Nano microsphere is in preparation process, by adding NaHCO3Buffer solution
Particle diameter containing aldehyde radical Nano microsphere is regulated and controled by concentration, and effect is notable；
(4) selected materials of the present invention is simple and easy to get, prepare the Nano microsphere method therefor in aldehyde radical is that industrialization is the most extensive
The emulsion polymerization technology used, is easier to realize industrialized production；
(5) present invention aldehyde radical containing aldehyde radical Nano microsphere and the amino in streptococcus acidi lactici Nisin are by Schiff coupling,
Obtain streptococcus acidi lactici conjugate, be possible not only to avoid the high temperature deactivation of streptococcus acidi lactici Nisin, enhanced stability, and
And add in packaging film as a kind of functional component, it is also possible to strengthen the compatibility with packaging film, pack in active antibacterial
Film has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture containing aldehyde radical Nano microsphere of preparation, wherein styrene and 4-in shell monomer in embodiment 1
The relationship between quality of vinylbenzaldehyde is 0:4g；
Fig. 2 is the gel permeation chromatography containing aldehyde radical Nano microsphere (GPC) of preparation in embodiment 1, and wherein A represents pure
Styrene, B represents the emulsion copolymers of styrene and 4-vinylbenzaldehyde, and operation condition is identical；
Fig. 3 be in embodiment 1 preparation containing aldehyde radical Nano microsphere and containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate
Infrared spectrogram, wherein, A is pure styrene；B represents the emulsion copolymers of styrene and 4-vinylbenzaldehyde,
Both operation conditions are identical；After C is B load Nisin；
Fig. 4 is the transmission electron microscope picture containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate of preparation in embodiment 4.
Detailed description of the invention
The present invention is described in further detail for the embodiment be given below in conjunction with inventor, each component below used,
As indicated without special, it is commercially available.
Embodiment 1
The present embodiment provide particle diameter adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere, this contains aldehyde radical Nano microsphere
Particle diameter is 173nm, and dispersion is 0.2, and the nuclear monomer containing aldehyde radical Nano microsphere is styrene, and shell monomer is 4-vinyl
Benzaldehyde VBA, wherein the proportion by weight of nuclear monomer and shell monomer is 4:1.
This particle diameter is adjustable, and to have the preparation method containing aldehyde radical Nano microsphere of nucleocapsid structure as follows:
(1) emulsifying agent and the screening of initiator and preparation
In amphoteric emulsifier, conventional has DNS-86, DNS-268 and DNS-458, but when using the above two to be polymerized,
Thus obtained microsphere is unstable, easily assembles, and this is likely due to what emulsifying the most thoroughly caused, in consideration of it, select DNS-458
(buy in Guangzhou double bond trade Co., Ltd, the most only enumerate, be not defined, other commercially available prod also can),
It is effective, and thus obtained microsphere is stable, it is not easy to assemble, account for core, the 3.35% of shell monomer amount gross mass, accurately weigh
0.67gDNS-458 is dissolved in 64mL deionized water, configures emulsifier solution.
Select Ammonium persulfate. (APS) as initiator, account for core, the 1.6% of shell monomer gross mass, weigh 0.32g APS
It is dissolved in 12mL deionized water, is configured to the APS solution of 12mL.
(2) core emulsion and the pre-emulsification of shell emulsion
Presenting inertia inside polymer microballoon, outside containing active functional group, the surface being supported on spheroid is carried out, not only
Can improve efficiency, cost-effective, and beneficially the stablizing of microsphere.Styrene (St) and 4-vinylbenzaldehyde
The framing structure phase of VBA (VBA, Wulff G, Akelah A.Makromol Chem 1979,179:2647～2651)
Seemingly, the compatibility is preferable, and after polymerization, styrene is inert.In consideration of it, selecting St is nuclear monomer, VBA is shell monomer,
The proportion by weight of the two is 4:1.
For making micro-sphere structure stable, compacting, add cross-linking monomer, conventional cross-linking monomer has divinylbenzene (DVB)
With AMA (Guangzhou one horse reagent company limited, purity: 99%, the most only enumerate, be not defined, other
Commercially available prod also can), but find that DVB thus obtained microsphere is unstable by preliminary experiment, and use AMA thus obtained microsphere steady
Fixed, so, select AMA as cross-linking monomer, account for nuclear monomer styrene and shell monomer 4-vinylbenzaldehyde gross mass
1%.
Therefore, core emulsion consist of St 16g, AMA 0.16g, DNS-458 44mL；Shell emulsion consist of VBA
4g、AMA 0.04g、DNS-458 14mL.Respectively by the core emulsion configured and shell emulsion in 250mL conical flask
In, mechanical agitation (rotating speed 570rmp) carries out pre-emulsification, about 15min, and emulsion is off-white color, after standing 15min
Without lamination.
(3) synthesis of seed emulsion styrene core
0.01gNaHCO is added in 250mL reaction bulb3Buffer solution, 10mL water, 6mLDNS-458 solution and
10mL core pre-emulsion, and quickly stirring (rotating speed is 600～700rmp) 3min, then oil bath heating, mechanical agitation
Speed will be for 285rmp；In time being warming up to 70 DEG C, add 5mL APS, then heat to 78 DEG C, react about 20～30min,
Reactant blueing light, continues reaction 10min, then dropping residue the core pre-emulsion of 46mL, 3mL APS solution, control
Make in 1～1.5h dropping complete；Continuing reaction 10min, specifically, mixing speed can not be too big, otherwise, and microsphere
Uniformity be deteriorated, its two, the particle diameter of microsphere passes through NaHCO3The concentration of buffer solution regulates and controls, and effect is notable.
(4) the emulsion polymerization of VBA shell
In the reaction system of above-mentioned 78 DEG C, the 16mL shell pre-emulsion of preparation, 2mL APS in dropping step (2)
Solution, controls to drip in 0.5～1h complete, after continuing reaction 10min, drips remaining 2mLAPS solution,
It is warming up to 85 DEG C, reacts 1h, with ammonia regulation pH value to neutral, without styrene taste.
It is 173nm that particle size determination instrument measures the particle diameter of gained latex ion, and dispersion is 0.2, enters one by transmission electron microscope
Step observes its pattern (Fig. 1), and result shows the Nano microsphere structure that size is homogeneous, structure is clear and definite, the big I of its particle diameter
To pass through NaHCO3The addition of solution is adjusted；Gel permeation chromatography (GPC) data show (Fig. 2) copolymerization
Rear molecular weight hoists movement, and number-average molecular weight Mn of pure styrene is 111549, and monodispersity PDI is 1.5, and
After copolymerization, Mn is 165655, and PDI is 1.35, and is all typical Gauss distribution, for unimodal, shows styrene and 4-
Vinylbenzaldehyde there occurs effective copolymerization；Ir data shows (B in Fig. 3), and copolymer is at 2782-2886cm-1
There is double-absorption peak, at 1710cm-1There is single absworption peak, it was demonstrated that the existence of aldehyde radical.
Embodiment 2
The present embodiment provide particle diameter adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere, this contains aldehyde radical Nano microsphere
Particle diameter is about 300nm, and dispersion is 0.202, and the nuclear monomer containing aldehyde radical Nano microsphere is styrene, and shell monomer is 4-second
Alkenyl benzene formaldehyde VBA and styrene St, wherein the proportion by weight of nuclear monomer and shell monomer is 4:1,4-in shell monomer
The proportion by weight of vinylbenzaldehyde VBA and styrene St is 1:6.
This particle diameter is adjustable has the preparation method containing aldehyde radical Nano microsphere of nucleocapsid structure as different from Example 1:
The consumption of cross-linking monomer is nuclear monomer and the 0.5% of shell monomer gross mass.
The consumption of emulsifying agent is nuclear monomer and the 5% of shell monomer gross mass, and in its center emulsion, the consumption of cross-linking monomer is
The 82% of cross-linking monomer gross mass, the consumption of emulsifying agent is the 70% of emulsifying agent gross mass, in shell emulsion, cross-linking monomer
Consumption is the 18% of cross-linking monomer gross mass, and the consumption of emulsifying agent is the 20% of emulsifying agent gross mass.
Initiator is Ammonium persulfate., and its consumption is nuclear monomer and the 1% of shell monomer gross mass.
During the pre-emulsification of core emulsion and shell emulsion, rotating speed during stirring is 500rmp, and mixing time is 20min, during standing
Between be 20min.
During the synthesis of seed emulsion styrene core, the consumption of part core pre-emulsion accounts for the 15% of total core pre-emulsion, NaHCO3
The consumption of buffer solution is nuclear monomer styrene and the 0.5% of shell monomer 4-vinylbenzaldehyde gross mass, and the consumption of water is
2 times of part core pre-emulsion, emulsifying agent is DNS-458, and its consumption is the 10% of emulsifying agent gross mass.
During the synthesis of seed emulsion styrene core, quickly rotating speed during stirring is 600rpm, and mixing time is 4min, oil
During bath heating, the rotating speed of stirring at low speed is 100rpm, and during bottoming, reaction temperature is 65 DEG C, and it is total that initiator amount accounts for initiator
The 60% of quality, is continuously heating to 70 DEG C of reaction 30min, to reactant blueing light, continues reaction 20min, then drips
Adding residual nucleus pre-emulsion and account for the initiator of initiator gross mass 10%, time for adding controls 1～1.5h, continues reaction
10～20min, prepare seed emulsion styrene core.
During hud polymerization, the consumption of initiator accounts for the 10% of initiator gross mass, controls to drip in 0.5～1h complete,
Continue reaction 10min.
During strengthening, being warming up to 75 DEG C, react 2h, initiator amount accounts for initiator gross mass 20%.
Embodiment 3
The present embodiment provide particle diameter adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere, this contains aldehyde radical Nano microsphere
Particle diameter is about 120nm, and dispersion is 0.15, and the nuclear monomer containing aldehyde radical Nano microsphere is styrene, and shell monomer is 4-second
Alkenyl benzene formaldehyde VBA and styrene St, wherein the proportion by weight of nuclear monomer and shell monomer is 4:1,4-in shell monomer
The proportion by weight of vinylbenzaldehyde VBA and styrene St is 1:8.
This particle diameter is adjustable has the preparation method containing aldehyde radical Nano microsphere of nucleocapsid structure as different from Example 1:
The consumption of cross-linking monomer is nuclear monomer and the 1.5% of shell monomer gross mass.
The consumption of emulsifying agent is nuclear monomer and the 3% of shell monomer gross mass；In its center emulsion, the consumption of cross-linking monomer is
The 78% of cross-linking monomer gross mass, the consumption of emulsifying agent is the 65% of emulsifying agent gross mass, in shell emulsion, cross-linking monomer
Consumption is the 22% of cross-linking monomer gross mass, and the consumption of emulsifying agent is the 22% of emulsifying agent gross mass.
Initiator is Ammonium persulfate., and its consumption is nuclear monomer and the 2% of shell monomer gross mass.
During the pre-emulsification of core emulsion and shell emulsion, rotating speed during stirring is 600rmp, mixing time 10min, time of repose
For 10min.
During the synthesis of seed emulsion styrene core, the consumption of part core pre-emulsion accounts for the 20% of total core pre-emulsion, without adding
NaHCO3Buffer solution, the consumption of water is 1.5 times of part core pre-emulsion, and emulsifying agent is DNS-458, and its consumption is
The 13% of emulsifying agent gross mass.
During the synthesis of seed emulsion styrene core, quickly rotating speed during stirring is 700rpm, and mixing time is 2min, oil
During bath heating, the rotating speed of stirring at low speed is 400rpm, and during bottoming, reaction temperature is 70 DEG C, and it is total that initiator amount accounts for initiator
The 30% of quality, is continuously heating to 80 DEG C of reaction 20min, to reactant blueing light, continues reaction 10min, then drips
Adding residual nucleus pre-emulsion and account for the initiator of initiator gross mass 30%, time for adding controls 1～1.5h, continues reaction
10～20min, prepare seed emulsion styrene core.
During hud polymerization, the consumption of initiator accounts for the 30% of initiator gross mass, controls to drip in 0.5～1h complete,
Continue reaction 10min.
During strengthening, being warming up to 90 DEG C, react 1h, initiator amount accounts for initiator gross mass 10%.
Embodiment 4
The present embodiment provide containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate, use the particle diameter of preparation in embodiment 1
The adjustable Nano microsphere containing aldehyde radical with nucleocapsid structure is made with streptococcus acidi lactici.
Concrete preparation process is: the 60mL emulsion microsphere of Example 1 preparation, with the lactic acid chain of 80mL10mg/mL
The solution mixing of coccus, the speed concussion 24h of 100rpm, ultracentrifugation, take the supernatant, ultraviolet surveys absorbance, enters
And calculate its load capacity, and remove unreacted streptococcus acidi lactici, in triplicate, freezer dryer is dried, and must contain aldehyde radical
Nano microsphere-streptococcus acidi lactici conjugate (alternatively referred to as 4-vinylbenzaldehyde-streptococcus acidi lactici), load factor is 95%,
It is 256nm that particle size analyzer measures the particle diameter of gained conjugate, and dispersion is 0.2, and transmission electron microscope (see Fig. 4) display is sewed
Compound structure spherical in shape, size are homogeneous, and the size of its particle diameter can be by containing NaHCO in aldehyde radical Nano microsphere preparation process3
The addition of solution is adjusted；Infrared spectrum (see C in Fig. 3) data show at 1730cm-1The feature of neighbouring aldehyde
Peak weakens, and corresponding at 3063cm-1Place occurs in that the characteristic absorption peak of imines, additionally, 1614-1620cm-1?
In the range of go out to have stretching vibration peak, it was demonstrated that the existence of Schiff.Make containing aldehyde radical Nano microsphere-streptococcus acidi lactici
Conjugate can add in packaging film as a kind of functional component, it is also possible to strengthens the compatibility with packaging film, in activity
Anti-bacterial packaging film has a good application prospect.
Embodiment 5
The present embodiment provide containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate, use the particle diameter of preparation in embodiment 2
The adjustable Nano microsphere containing aldehyde radical with nucleocapsid structure is made with streptococcus acidi lactici.
Concrete preparation process is: the 60mL emulsion microsphere of Example 2 preparation, with the lactic acid chain of 40mL10mg/mL
The solution mixing of coccus, the speed concussion 30h of 90rpm, ultracentrifugation, take the supernatant, ultraviolet surveys absorbance, enters
And calculate its load capacity, and remove unreacted streptococcus acidi lactici, in triplicate, freezer dryer is dried, and must contain aldehyde radical
Copolymer nanometer microsphere-streptococcus acidi lactici conjugate.
Embodiment 6
The present embodiment provide containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate, use the particle diameter of preparation in embodiment 3
The adjustable Nano microsphere containing aldehyde radical with nucleocapsid structure is made with streptococcus acidi lactici.
Concrete preparation process is: the 60mL emulsion microsphere of Example 2 preparation, with the lactic acid chain of 20mL10mg/mL
The solution mixing of coccus, the speed concussion 10h of 110rpm, ultracentrifugation, take the supernatant, ultraviolet surveys absorbance, enters
And calculate its load capacity, and remove unreacted streptococcus acidi lactici, in triplicate, freezer dryer is dried, and obtains aldehyde radical altogether
Polymers Nano microsphere-streptococcus acidi lactici conjugate.
The present invention aldehyde radical containing aldehyde radical Nano microsphere and the amino in streptococcus acidi lactici Nisin are by Schiff coupling, it is thus achieved that
Streptococcus acidi lactici conjugate, is possible not only to avoid the high temperature deactivation of streptococcus acidi lactici Nisin, enhanced stability, Er Qiezuo
Add in packaging film for a kind of functional component, it is also possible to strengthen the compatibility with packaging film, in active antibacterial packaging film
Have a good application prospect.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by above-described embodiment
System, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, letter
Change, all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (10)
1. particle diameter adjustable have nucleocapsid structure containing an aldehyde radical Nano microsphere, it is characterized in that: this contains aldehyde radical
The particle diameter of Nano microsphere is 100～305nm, and dispersion is 0.1～0.202, the described core containing aldehyde radical Nano microsphere
Monomer is styrene, and shell monomer is 4-vinylbenzaldehyde, or shell monomer is styrene and 4-vinyl benzene first
The mix monomer of aldehyde, the proportion by weight of described nuclear monomer and described both shell monomers is 4:1.
2. the adjustable preparation side containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter described in claim 1
Method, is characterized in that comprising the following steps:
(1) preparation core emulsion and shell emulsion: core emulsion is made up of nuclear monomer, cross-linking monomer and emulsifying agent, shell
Emulsion is made up of shell monomer, cross-linking monomer and emulsifying agent；
(2) core emulsion and the pre-emulsification of shell emulsion: by the core emulsion prepared in step (1) and shell emulsion difference
Stirring carries out pre-emulsification, obtains core pre-emulsion respectively and shell pre-emulsion is standby after standing；
(3) synthesis of seed emulsion styrene core: choose NaHCO3Buffer solution, water, emulsifying agent and portion
Pyrene pre-emulsion, quickly after stirring, oil bath is heated, stirring at low speed simultaneously, adds and account for when being warming up to 65～70 DEG C
Initiator gross mass 30～the initiator bottoming of 60%, be continuously heating to 70～80 DEG C of reactions 20～30min, to instead
Answer thing blueing light, continue reaction 10～20min, then drip residual nucleus pre-emulsion and account for initiator gross mass
10～the initiator of 30%, time for adding controls 1～1.5h, continues reaction 10～20min, prepares seed emulsion
Styrene core；
(4) hud polymerization: add in step (1) in the seed emulsion styrene core that step (3) prepares
Shell pre-emulsion and account for initiator gross mass 10～the initiator of 30%, control to drip in 0.5～1h complete, continue
After continuous reaction 10～20min, obtain core-shell emulsion；
(5) strengthening: drip remaining initiator in core-shell emulsion prepared by step (4), be warming up to
75～90 DEG C, reacting 1～2h, regulation pH value is to neutral, and products therefrom is that particle diameter is adjustable has nucleocapsid knot
Structure containing aldehyde radical Nano microsphere.
The adjustable system containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter the most according to claim 2
Preparation Method, is characterized in that: nuclear monomer described in step (1) is 4:1 with the proportion by weight of shell monomer, described
Cross-linking monomer is AMA, and its consumption is nuclear monomer and the 0.5 of shell monomer gross mass～1.5%, and described emulsifying agent is
DNS-458, its consumption is nuclear monomer and the 2 of shell monomer gross mass～5%；In its center emulsion, cross-linking monomer
Consumption is cross-linking monomer gross mass 78～82%, the consumption of emulsifying agent is the 65～70% of emulsifying agent gross mass,
In shell emulsion, the consumption of cross-linking monomer is the 18～22% of cross-linking monomer gross mass, and the consumption of emulsifying agent is emulsifying
The 20～22% of agent gross mass.
The adjustable system containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter the most according to claim 2
Preparation Method, is characterized in that: in step (2), rotating speed during stirring is 500～600rmp, and mixing time is
10～20min；Time of repose is 10～20min.
The adjustable system containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter the most according to claim 2
Preparation Method, is characterized in that: the consumption of step (3) middle part pyrene pre-emulsion accounts for the 15～20% of total core pre-emulsion,
NaHCO3The consumption of buffer solution is nuclear monomer and the 0 of shell monomer gross mass～1%, and the consumption of water is part core
1～2 times of pre-emulsion, described emulsifying agent is DNS-458, and its consumption is the 8～13% of emulsifying agent gross mass.
The adjustable system containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter the most according to claim 2
Preparation Method, is characterized in that: rotating speed when quickly stirring in step (3) is 600～700rpm, and mixing time is
2～4min, during oil bath heating, the rotating speed of stirring at low speed is 100～400rpm.
The adjustable system containing aldehyde radical Nano microsphere with nucleocapsid structure of particle diameter the most according to claim 2
Preparation Method, is characterized in that: the initiator described in step (3)～step (5) is Ammonium persulfate., its consumption
For nuclear monomer and the 1 of shell monomer gross mass～2%, step (5) using ammonia regulation pH the most neutral, without benzene
Ethylene taste.
8. containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate, it is characterized in that: use claim 1 institute
The particle diameter stated is adjustable have nucleocapsid structure containing aldehyde radical Nano microsphere or claim 2-7 any one preparation method
The Nano microsphere containing aldehyde radical made is made with streptococcus acidi lactici.
9. the preparation method containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate described in claim 8, it is special
Levy is to comprise the following steps: the particle diameter of choosing in claim 1 is adjustable have nucleocapsid structure containing aldehyde radical nanometer
Microsphere or claim 2-7 any one preparation method make containing aldehyde radical Nano microsphere, with streptococcus acidi lactici solution
After mixing, vibrate, be centrifuged, take the supernatant, the most i.e. prepare containing aldehyde radical Nano microsphere-streptococcus acidi lactici
Conjugate.
Preparation method containing aldehyde radical Nano microsphere-streptococcus acidi lactici conjugate the most according to claim 9,
It is characterized in that: vibration uses shaking table vibration, and hunting speed is 70～110rpm, and duration of oscillation is 10～30h.
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