CN104387539B - A kind of fluorescent carbon nano-particle hybrid microgel of pH response and preparation method thereof - Google Patents
A kind of fluorescent carbon nano-particle hybrid microgel of pH response and preparation method thereof Download PDFInfo
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- 239000011852 carbon nanoparticle Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000000502 dialysis Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000010926 purge Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical group ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 239000000385 dialysis solution Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000001139 pH measurement Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 230000003313 weakening effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
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Abstract
A kind of fluorescent carbon nano-particle hybrid microgel of pH response and preparation method thereof, including: (1) weighs fluorescent carbon nano-particle, dissolves preparation fluorescent carbon nanoparticles solution with dichloromethane, add acyl chloride monomer, at room temperature react 10h, remove reaction dissolvent, add water, be spin-dried for;(2) double bond fluorescent carbon nano-particle is weighed to obtain, it is added in distilled water, and transfer in reaction vessel, cross-linking agent, dodecyl sodium sulfate and pH responsive polymer monomer is added after air-out, logical nitrogen is to get rid of air, heating, after question response liquid starts backflow, adds initiator in there-necked flask;(3) maintaining nitrogen purge stirring, at 50 90 DEG C of back flow reaction 5 20h;(4) filter after being cooled to room temperature, take filtrate, take filtrate and be placed in bag filter dialysis 48h.The product inanimate object toxicity that the present invention prepares, its particle diameter is at about 760nm, and under Same Wavelength excites, fluorescence has good pH response, has well application at drug release, pH sensing, catalytic field.
Description
Technical field
The present invention relates to chemical technology field, particularly to the response fluorescent carbon nano-particle hybrid microgel and preparation method thereof of a kind of pH.
Technical background
Microgel (microgel) is the polymeric colloid particle that intramolecular is highly cross-linked, and its internal structure is typical tridimensional network.Microgel (hydrogel) is a kind of to save large quantity of moisture and the most swelling hydrophilic gel.Because structure typically contains hydrophilic group, such as-CONH2、-COOH、-SO3H etc., these microgels are generally of environment (such as pH, temperature) stimuli responsive performance, and its volume can be grown up along with the change of environment (such as pH, temperature) or reduce.Because of various features such as micro-gel surface absorption property are strong, specific surface area big, functional diversity, gel particle size are controlled, structure composition can design so that it is have the most potential using value in various fields such as medicine transmission, civil construction, food fresh keeping, fire-fighting, sewage disposals.But, existing response microgel often only has volume response, i.e. during environmental change, is generally only its volume and responds environmental change, this greatly limits the actual application of hydrogel.Therefore, utilize new material new method to design and prepare novel response microgel, can preferably apply a lot of field, develop one of novel response microgel focus direction also becoming research hydrogel field.
Summary of the invention
Invention provides the fluorescent carbon nano-particle hybrid microgel of a kind of pH response, and the fluorescence of this fluorescent carbon nano-particle hybrid microgel has good pH response, has well application at pH sensing, drug release, catalytic field.
For achieving the above object, embodiment of the present invention are: the preparation method of the fluorescent carbon nano-particle hybrid microgel of a kind of pH response, comprise the following steps:
(1) weigh fluorescent carbon nano-particle, dissolve with dichloromethane, be configured to the fluorescent carbon particle solution that concentration is 0.5-10mg/mL, add acyl chloride monomer, at room temperature react 10h, afterwards reaction dissolvent is removed, add water, after being spin-dried for, obtain double bond fluorescent carbon nano-particle;
(2) weigh double bond fluorescent carbon nano-particle, add dispersing and dissolving in 100mL distilled water;And be transferred in the there-necked flask equipped with agitator, reflux condensing tube and thermometer;Open agitator, and uniformly lead to nitrogen, after being completely exhausted out the air in container and solution, add cross-linking agent, dodecyl sodium sulfate (SDS), pH responsive polymer monomer;Continue logical nitrogen, be completely exhausted out the air in container and solution, heating;After question response liquid starts backflow, weigh initiator and be added in there-necked flask;
(3) maintaining nitrogen purge, stopped reaction after continuing back flow reaction 5-20h at 50-90 DEG C;
(4) filtering after being cooled to room temperature, take filtrate, take filtrate and be placed in bag filter dialysis 48h, gained dialysis solution is the carbon nano-particle hybrid microgel that purification is good.
In step (1), the mass ratio of described fluorescent carbon granule and acyl chloride monomer is 10:1-50:1.
In step (1), described fluorescent carbon nano-particle is fluorescent carbon nano-particle prepared by hydro-thermal method carbonization glucose, cellulose, chitosan, EDTA 2Na, EDTA or gelatin.It is preferably fluorescent carbon nano-particle prepared by hydro-thermal method carbonization EDTA 2Na.
In step (1), described acyl chloride monomer is acryloyl chloride, methacrylic chloride or crotonyl chloride.Preferably acryloyl chloride.
In step (2), described pH responsive polymer monomer is acrylic acid, methacrylic acid or acrylamide.Preferably acrylic acid.
In step (2), double bond fluorescent carbon amount of particles is 1-40 weight portion, and pH responsive polymer monomer consumption is 120-650 weight portion, and dodecyl sodium sulfate consumption is 1-20 weight portion, and initiator amount is 1-10 weight portion.Double bond fluorescent carbon granule is 1:3-1:650 with the mass ratio that feeds intake of pH responsive polymer monomer;Further preferably, double bond fluorescent carbon granule is 1:20 with the mass ratio that feeds intake of pH responsive polymer monomer.
In step (2), described initiator is hydrogen peroxide, Ammonium persulfate. or potassium peroxydisulfate.Preferably potassium peroxydisulfate.
In step (2), described cross-linking agent is N-N methylene-bisacrylamide.
In step (3), preferably back flow reaction temperature is 70 DEG C, and the response time is 10h.
The present invention also provides for the fluorescent carbon nano-particle hybrid microgel product that a kind of pH prepared such as said method responds.
The fluorescent carbon nano-particle hybrid microgel inanimate object toxicity of the pH response that invention prepares, its particle diameter is at about 760nm, and under Same Wavelength (320 nm) excites, pH increases, fluorescent weakening;Otherwise Fluorescence Increasing, fluorescence has good pH response;Well application is had at drug release, pH sensing, catalytic field.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope collection of illustrative plates (mean diameter is about 760 nm) of the fluorescent carbon nano-particle hybrid microgel of the pH response of embodiment 3 preparation
Fig. 2 is the pH response fluorescence pattern (pH increases, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength 320 nm) of the fluorescent carbon nano-particle hybrid microgel aqueous solution of embodiment 1 preparation.
Fig. 3 is the pH response fluorescence pattern (pH increases, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength 320 nm) of the fluorescent carbon nano-particle hybrid microgel aqueous solution of embodiment 2 preparation.
Fig. 4 is the pH response fluorescence pattern (pH increases, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength 320 nm) of the fluorescent carbon nano-particle hybrid microgel aqueous solution of embodiment 3 preparation.
Detailed description of the invention
The present invention is the most exemplarily described in detail below in conjunction with non-limiting specific embodiment.Reagent used in the embodiment of the present invention is except fluorescent carbon nano-particle is (according to Liao B.; Long, P.; He, B.; Yi, S.; Ou, B.; Shen, S.; Chen, J. J Mater
Chem C 2013, prepares described in 1,3716), remaining is the most commercially available obtains.
Embodiment 1:
Weigh appropriate fluorescent carbon nano-particle 100mg, dissolve with dichloromethane, be configured to the fluorescent carbon particle solution that concentration is 0.5-10mg/mL, add acryloyl chloride 4mg, at room temperature react 10h, afterwards reaction dissolvent is removed, add water, after being spin-dried for, obtain the fluorescent carbon nano-particle of double bond.
Weigh double bond fluorescent carbon granule 40mg, add in 20mL distilled water, and be transferred in the there-necked flask equipped with agitator, reflux condensing tube and thermometer.Open agitator, and uniformly lead to nitrogen, be completely exhausted out the air in container and solution.Add the refined acrylic acid of 5mg cross-linking agent N-N methylene-bisacrylamide, 5mg dodecyl sodium sulfate (SDS) and 600mg.Continue logical nitrogen, be completely exhausted out the air in container and solution.Heating, after question response liquid starts backflow, weighs 5mg potassium peroxydisulfate and adds in there-necked flask.Maintaining nitrogen purge, stopped reaction after continuing back flow reaction 18h at 80 DEG C, filter after being cooled to room temperature, take filtrate and be placed in bag filter dialysis 48h, gained dialysis solution is the carbon nano-particle hybrid microgel of the good pH response of purification.
Embodiment 2:
Weigh appropriate fluorescent carbon nano-particle 100mg, dissolve with dichloromethane, be configured to the fluorescent carbon particle solution that concentration is 0.5-10mg/mL.Add acryloyl chloride 4mg.At room temperature react 10h, afterwards reaction dissolvent is removed, add water, after being spin-dried for, obtain the fluorescent carbon nano-particle of double bond.
Weigh double bond fluorescent carbon granule 35mg, add in 100mL distilled water, and be transferred in the there-necked flask equipped with agitator, reflux condensing tube and thermometer.Open agitator, and uniformly lead to nitrogen, be completely exhausted out the air in container and solution.Add the refined acrylic acid of 8mg cross-linking agent N-N methylene-bisacrylamide, 10mg dodecyl sodium sulfate (SDS) and 550mg.Continue logical nitrogen, be completely exhausted out the air in container and solution.Heating, after question response liquid starts backflow, weighs 10 mg potassium peroxydisulfates and adds in there-necked flask.Maintaining nitrogen purge, stopped reaction after continuing back flow reaction 8h at 60 DEG C, filter after being cooled to room temperature, take filtrate and be placed in bag filter dialysis 48h, gained dialysis solution is the carbon nano-particle hybrid microgel of the good pH response of purification.
Embodiment 3:
Weigh appropriate fluorescent carbon nano-particle 100mg, dissolve with dichloromethane, be configured to the fluorescent carbon particle solution that concentration is 0.5-10mg/mL.Add acryloyl chloride 5mg.At room temperature react 10h, afterwards reaction dissolvent is removed, add water, after being spin-dried for, obtain the fluorescent carbon nano-particle of double bond.
Weigh double bond fluorescent carbon granule 30mg, add in 100mL distilled water, and be transferred in the there-necked flask equipped with agitator, reflux condensing tube and thermometer.Open agitator, and uniformly lead to nitrogen, be completely exhausted out the air in container and solution.Add the refined acrylic acid of 10mg cross-linking agent N-N methylene-bisacrylamide, 10mg dodecyl sodium sulfate (SDS) and 600mg.Continue logical nitrogen, be completely exhausted out the air in container and solution.Heating, after question response liquid starts backflow, weighs 5mg potassium peroxydisulfate and adds in there-necked flask.Maintaining nitrogen purge, stopped reaction after continuing back flow reaction 10h at 70 DEG C, filter after being cooled to room temperature, take filtrate and be placed in bag filter dialysis 48h, gained dialysis solution is the carbon nano-particle hybrid microgel of the good pH response of purification.
Claims (9)
1. the preparation method of the fluorescent carbon nano-particle hybrid microgel of a pH response, it is characterised in that comprise the following steps:
(1) fluorescent carbon nano-particle is weighed, dissolve with dichloromethane, it is configured to the fluorescent carbon particle solution that concentration is 0.5-10mg/mL, add acyl chloride monomer, at room temperature react 10h, afterwards reaction dissolvent is removed, add water, being spin-dried for obtaining double bond fluorescent carbon nano-particle, described acyl chloride monomer is acryloyl chloride, methacrylic chloride or crotonyl chloride;
(2) weigh double bond fluorescent carbon nano-particle, add dispersing and dissolving in 100mL distilled water;And be transferred in the there-necked flask equipped with agitator, reflux condensing tube and thermometer;Open agitator, and uniformly lead to nitrogen, it is completely exhausted out the air in container and solution, adds cross-linking agent, dodecyl sodium sulfate, pH responsive polymer monomer, continue logical nitrogen, it is completely exhausted out the air in container and solution, heating, after reactant liquor backflow, dissolves initiator in water, and add in there-necked flask, it is sufficiently stirred for;
(3) maintaining nitrogen purge, stopped reaction after continuing back flow reaction 5-20h at 50-90 DEG C;
(4) filtering after being cooled to room temperature, take filtrate, take filtrate and be placed in bag filter dialysis 48h, gained dialysis solution is the carbon nano-particle hybrid microgel that purification is good.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterised in that in step (1), the mass ratio of described fluorescent carbon granule and acyl chloride monomer is 10:1-50:1.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterized in that, in step (1), described fluorescent carbon nano-particle is fluorescent carbon nano-particle prepared by hydro-thermal method carbonization glucose, cellulose, chitosan, EDTA 2Na, EDTA or gelatin.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterised in that in step (2), described pH responsive polymer monomer is acrylic acid, methacrylic acid or acrylamide.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterized in that, in step (2), double bond fluorescent carbon amount of particles is 1-40 weight portion, pH responsive polymer monomer consumption is 120-650 weight portion, dodecyl sodium sulfate consumption is 1-20 weight portion, and initiator amount is 1-10 weight portion.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterised in that in step (2), double bond fluorescent carbon granule is 1:20 with the mass ratio that feeds intake of pH responsive polymer monomer.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterised in that in step (2), described initiator has hydrogen peroxide, Ammonium persulfate. or potassium peroxydisulfate.
The preparation method of the fluorescent carbon nano-particle hybrid microgel of pH the most according to claim 1 response, it is characterised in that in step (3), back flow reaction optimum temperature is 70 DEG C, and optimum reacting time is 10h.
9. the fluorescent carbon nano-particle hybrid microgel of the pH response that prepared by the method for claim 1.
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