CN104356576A - Preparation method of glucose responsive graphene/polymer nanometer hybrid material - Google Patents
Preparation method of glucose responsive graphene/polymer nanometer hybrid material Download PDFInfo
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Abstract
The invention belongs to the field of smart materials and nanomaterials, and particularly relates to a preparation method of glucose responsive graphene nanometer hybrid material. The method comprises the specific steps as follows: enabling 1-pyrene methyl alcohol and 2-bromine isobutyryl bromine to react to obtain pyrene methyl alcohol (Py-Br) end capped with a bromine atom; taking the Py-Br as an initiator to initiate the atom transfer radical polymerization of a monomer, namely (2-benzene boric acid ester-1,3-dioxane-5-ethyl) acrylic ester (PBDEMA), to obtain a poly-(2-benzene boric acid ester-1,3-dioxane-5-ethyl) acrylic ester (Py-PPBDEMA) material; then adding graphene into the Py-PPBDEMA solution, coupling a Py-PPBDEMA molecule on the surface of the graphene to form the graphene-Py-PPBDEMA nanometer hybrid material. The graphene nanometer hybrid material prepared by the invention is glucose-responsive, and is widely applied to the fields of intelligent sensors, biological nanometer devices and the like. The synthesis method is simple and feasible and has excellent popularization and application values, and all the materials can be industrially produced.
Description
Technical field
The invention belongs to intelligent material and field of nanometer material technology, be specifically related to a kind of preparation method of Graphene/Nano-hybrid polymeric materials of sugar response.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.But because Graphene has very large specific surface area, be easy to reunite, dispersiveness is in the solution poor, seriously limit its application.In addition, Graphene is inorganic materials, needs to carry out organically-modified to its surface, obtains inorganic-organic hybrid functional nano-materials, is beneficial to the function and application field expanding grapheme material.At present, the research preparing graphene oxide-polymer hybrid nano material by polymer graft to surface of graphene oxide is relatively many (as Zhu, C. H.; Lu, Y.; Peng. J.; Chen, J. F.; Yu, S. H.
adv. Funct. Mater.2012; 22:4017 – 22.); but at graphenic surface by non covalent bond as π-π coupling; and it is less to obtain Graphene-organic hybrid nano material; as at graphenic surface by with 5; 10; 15,20-tetra-(1-methyl-4-pyridine) is porphyrin coupled prepares nano-hybrid material (Xu, Y. X.; Zhao, L.; Bai, H.; Hong, W. J.; Li, C.; Shi, G. Q.
j. Am. Chem. Soc.2009,131,13490-13497).
Intelligence organic materials obtains extensive concern in recent years, and these materials can stimulate to external world, as temperature, pH value, light, sugar, salt, ionic strength change etc. respond, are all widely used at nanosecond science and technology, biomedical sector.Wherein, sugar responsive materials be recently grow up and obtain pay attention to smart material, they can combine with glycan molecule (glucose, fructose etc.), realize the conversion of polymer segment from hydrophobic to hydrophilic, are conducive to the insulin molecule of load to discharge, be used for the treatment of (the Yuan Yao such as diabetes, Liyuan Zhao, Junjiao Yang and Jing Yang, Biomacromolecules 2012,13,1837-1844).Therefore, sugared responsive polymer is incorporated into graphenic surface, the graphene nano hybrid material of sugar response can be prepared.In the present invention, we are by forming the sugared Graphene/Nano-hybrid polymeric materials responded by pyrene end group sugar responsive polymer and Graphene π-π coupling.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene/Nano-hybrid polymeric materials of sugar response.
The object of the invention is, by 1-pyrene methyl alcohol and 2-bromine isobutyryl bromine reaction, to obtain the pyrene methyl alcohol (Py-Br) of bromine atoms end-blocking.Be initiator trigger monomer (2-borate ester-1 again with Py-Br, 3-dioxane-5-ethyl) atom transfer radical polymerization of acrylate (PBDEMA), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) material of pyrene end-blocking.In Py-PPBDEMA solution, add Graphene again, the coupling of Py-PPBDEMA molecule, at graphenic surface, forms Graphene-Py-PPBDEMA nano-hybrid material.
The preparation method of the Graphene/Nano-hybrid polymeric materials of the sugar response that the present invention proposes, concrete steps are as follows:
(1) 1-pyrene methyl alcohol is dissolved in dry solvent orange 2 A, adds the acid binding agent B of 1-pyrene moles of methanol 1 ~ 4 times, 0 ~ 5
othe 2-bromine isobutyl acylbromide of 1-pyrene moles of methanol 1 ~ 4 times is instilled, then 10 ~ 30 under C
oc also reacts 24 ~ 48 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.
(2) and with end group be the pyrene methyl alcohol (Py-Br) of bromine be initiator, under solvent C and catalyzer D system, 70 ~ 100
o(the 2-borate ester-1 of Py-Br mole number 60 ~ 120 times is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 30 ~ 60 hours, precipitate further by precipitation agent E, obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.
(3) Py-PPBDEMA solvent F is dissolved, and add Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
In the present invention, described solvent orange 2 A is one or more in methylene dichloride, chloroform, tetrahydrofuran (THF) or toluene.
In the present invention, described acid binding agent B is one or more in diethylamine, triethylamine, pyridine or sodium acetate.
In the present invention, described solvent C is one or more in tetrahydrofuran (THF), methyl-phenoxide, DMF or N, N-diethylformamide.
In the present invention, described catalyst system D is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or cuprous bromide/hexamethyl Triethylenetetramine (TETA).
In the present invention, described precipitation agent E is one or more of normal hexane, hexanaphthene, sherwood oil or ether.
In the present invention, described solvent F is one or more in tetrahydrofuran (THF), DMF or N, N-diethylformamide.
Beneficial effect of the present invention is: raw material sources are extensive, and monomer used, Graphene, solvent, catalyzer, precipitation agent etc. all can suitability for industrialized production, and synthetic method is simple.Graphene-Py-PPBDEMA the nano-hybrid material of preparation has sugared responsiveness.This hybrid material has a wide range of applications in fields such as nano-carrier, biological intelligence switch, biosensors.
Accompanying drawing explanation
Fig. 1 is that the structure of Graphene-Py-PPBDEMA nano-hybrid material prepared by embodiment 1 responds schematic diagram with sugar.
Embodiment
Following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
The 1-pyrene methyl alcohol of 0.232g is dissolved in dry methylene dichloride (60 mL), adds 0.101g acid binding agent triethylamine, 0
othe 2-bromine isobutyl acylbromide of 0.23g is instilled, then 10 under C
oc also reacts 48 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.With the Py-Br of 95.5mg for initiator, methyl-phenoxide (15mL) is solvent, and cuprous bromide/pentamethyl-diethylenetriamine is catalyst system, 70
o8.1g (2-borate ester-1 is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 60 hours, precipitate further by precipitation agent ether (100mL), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.1g Py-PPBDEMA tetrahydrofuran solvent is dissolved (50mL), and adds 50mg Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
Hydridization grapheme material size 300-600 nanometer, polymericular weight 13200 grams/mol in hybrid material
The structure of Graphene-Py-PPBDEMA nano-hybrid material responds schematic diagram as shown in Figure 1 with sugar.
Embodiment 2
The 1-pyrene methyl alcohol of 0.232g is dissolved in dry methylene dichloride (60 mL), adds 0.2g acid binding agent diethylamine, 3
othe 2-bromine isobutyl acylbromide of 0.46g is instilled, then 15 under C
oc also reacts 40 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.With the Py-Br of 95.5mg for initiator, DMF (15mL) is solvent, and cuprous bromide/dipyridyl is catalyst system, 80
o6g (2-borate ester-1 is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 50 hours, precipitate further by precipitation agent sherwood oil (100mL), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.1g Py-PPBDEMA solvent DMF is dissolved (50mL), and adds 50mg Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
Graphene hybrid material size 280-500 nanometer, polymericular weight 10300 grams/mol in hybrid material.
Embodiment 3
The 1-pyrene methyl alcohol of 0.232g is dissolved in dry trichloromethane (60 mL), adds 0.202g acid binding agent triethylamine, 0
othe 2-bromine isobutyl acylbromide of 0.69g is instilled, then 20 under C
oc also reacts 30 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.With the Py-Br of 95.5mg for initiator, methyl-phenoxide (10mL) is solvent, and cuprous chloride/hexamethyl Triethylenetetramine (TETA) is catalyst system, 90
o5.6g (2-borate ester-1 is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 48 hours, precipitate further by precipitation agent normal hexane (100mL), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.1g Py-PPBDEMA tetrahydrofuran solvent is dissolved (50mL), and adds 50mg Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
Graphene hybrid material size 300-480 nanometer, polymericular weight 14500 grams/mol in hybrid material.
Embodiment 4
The 1-pyrene methyl alcohol of 0.232g is dissolved in dry toluene (60 mL), adds 0.3g acid binding agent sodium acetate, 5
othe 2-bromine isobutyl acylbromide of 0.8g is instilled, then 30 under C
oc also reacts 24 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.With the Py-Br of 95.5mg for initiator, methyl-phenoxide (12mL) is solvent, and cuprous bromide/hexamethyl Triethylenetetramine (TETA) is catalyst system, 100
o4.8g (2-borate ester-1 is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 30 hours, precipitate further by precipitation agent ether (100mL), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.By 1g Py-PPBDEMA N, N-diethylformamide dissolution with solvents (50mL), and add 50mg Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
Graphene hybrid material size 300-470 nanometer, polymericular weight 7800 grams/mol in hybrid material.
Embodiment 5
The 1-pyrene methyl alcohol of 0.232g is dissolved in dry tetrahydrofuran (THF) (60 mL), adds 0.404g acid binding agent triethylamine, 0
othe 2-bromine isobutyl acylbromide of 0.92g is instilled, then 30 under C
oc also reacts 24 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl.With the Py-Br of 95.5mg for initiator, methyl-phenoxide (10mL) is solvent, and cuprous bromide/pentamethyl-diethylenetriamine is catalyst system, 90
o4.05g (2-borate ester-1 is caused during C, 3-dioxane-5-ethyl) atom transfer radical polymerization (ATRP) of acrylate (PBDEMA) reacts 48 hours, precipitate further by precipitation agent ether (100mL), obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking.1g Py-PPBDEMA tetrahydrofuran solvent is dissolved (50mL), and adds 50mg Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
Graphene hybrid material size 350-560 nanometer, polymericular weight 7200 grams/mol in hybrid material.
Claims (7)
1. a preparation method for the Graphene/Nano-hybrid polymeric materials of sugar response, is characterized in that concrete steps are as follows:
(1) 1-pyrene methyl alcohol is dissolved in dry solvent orange 2 A, adds the acid binding agent B of 1-pyrene moles of methanol 1 ~ 4 times, 0 ~ 5
othe 2-bromine isobutyl acylbromide of 1-pyrene moles of methanol 1 ~ 4 times is instilled, then 10 ~ 30 under C
oc also reacts 24 ~ 48 hours under argon shield, obtains the pyrene methyl alcohol (Py-Br) that end group is acyl;
(2) end group obtained with step (1) be the pyrene methyl alcohol of bromine for initiator, under solvent C and catalyzer D system, 70 ~ 100
o(the 2-borate ester-1 of Py-Br mole number 60 ~ 120 times is caused during C, 3-dioxane-5-ethyl) atom transition free radical polymerization reaction 30 ~ 60 hours of acrylate, precipitate further by precipitation agent E, obtain poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate (Py-PPBDEMA) of pyrene end-blocking;
(3) pyrene-poly-(2-borate ester-1,3-dioxane-5-ethyl) acrylate solvent F is dissolved, and adds Graphene, at room temperature ultrasonic 1 hour, obtain the Graphene-Py-PPBDEMA nano-hybrid material disperseed.
2. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that described solvent orange 2 A is one or more in methylene dichloride, chloroform, tetrahydrofuran (THF) or toluene.
3. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that acid binding agent B is one or more in diethylamine, triethylamine, pyridine or sodium acetate.
4. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that described solvent C is one or more in tetrahydrofuran (THF), methyl-phenoxide, DMF or N, N-diethylformamide.
5. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that catalyst system D is one or more in cuprous chloride/dipyridyl, cuprous bromide/dipyridyl, cuprous chloride/pentamethyl-diethylenetriamine, cuprous bromide/pentamethyl-diethylenetriamine, cuprous chloride/hexamethyl Triethylenetetramine (TETA) or cuprous bromide/hexamethyl Triethylenetetramine (TETA).
6. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that precipitation agent E is one or more of normal hexane, hexanaphthene, sherwood oil or ether.
7. the preparation method of Graphene/Nano-hybrid polymeric materials of sugar response according to claim 1, is characterized in that described solvent F is one or more in tetrahydrofuran (THF), DMF or N, N-diethylformamide.
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| CN106832245A (en) * | 2017-01-23 | 2017-06-13 | 同济大学 | A kind of preparation method of the degradable films of sugared response |
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| CN103881040A (en) * | 2014-03-10 | 2014-06-25 | 同济大学 | Preparation method of temperature and CO2 double-responsive block copolymer nano micelle |
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Cited By (2)
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Application publication date: 20150218 |