CN117003914A - Preparation of chiral cyclic nanomaterial - Google Patents
Preparation of chiral cyclic nanomaterial Download PDFInfo
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- CN117003914A CN117003914A CN202310976723.4A CN202310976723A CN117003914A CN 117003914 A CN117003914 A CN 117003914A CN 202310976723 A CN202310976723 A CN 202310976723A CN 117003914 A CN117003914 A CN 117003914A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 42
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000502 dialysis Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 11
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 pentafluorophenol ester Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002983 circular dichroism Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 238000001142 circular dichroism spectrum Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical class OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/061—Chiral polymers
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a preparation method of chiral cyclic nano-materials, which relates to the field of biological chiral catalytic materials, and comprises the steps of firstly preparing a series of chiral liquid crystal block copolymers with different polymerization degrees through grafting reaction of pentafluorophenol ester and amino biphenyl liquid crystal molecules; the preparation of the annular nano material can be realized by adopting a cyclic dialysis method to assemble and changing the hydrophilic-hydrophobic block proportion and the assembling temperature of the polymer, and the chiral signal of the chiral annular nano material is controllable, thereby being beneficial to realizing high selectivity and high efficiency of chiral catalysis.
Description
Technical Field
The invention relates to the field of biological chiral catalytic materials, in particular to preparation of chiral annular nano materials.
Background
The living body is derived from chiral structural materials, almost all amino acids constituting the earth living body are left-handed amino acids, but no right-handed amino acids, and some saccharides, proteins and amino acids in the living body have a single chiral character, and the chiral character determines the basic functions in the living body. The property of chirality is introduced into self-assembly to develop chiral structure assembly materials, and the method has very important research significance for disclosing objective rules between chiral structures and functions.
The preparation of the chiral catalyst at the present stage is an important point in the practical application direction of the chiral field. Chiral catalyst materials are various, such as metal complex chiral materials, biological chiral catalytic materials, small organic molecule chiral catalytic materials, high molecular chiral catalytic materials and the like. The polymer chiral catalytic material combines the advantages of homogeneous phase and heterogeneous catalyst, the catalyst is simple to separate and can be recycled, and the chiral catalytic efficiency can be effectively improved due to the characteristic of polymer swelling, so that the development of a novel polymer chiral nano material is conducive to realizing high selectivity and high efficiency of chiral catalysis.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, provides a polymer with chiral characteristics and a preparation method thereof, and is applied to the preparation of chiral annular nano materials, and the prepared chiral annular nano materials have controllable chiral signals, thereby being beneficial to realizing high selectivity and high efficiency of chiral catalysis.
One of the purposes of the invention is to provide a polymer with chiral characteristics, which is specifically:
a polymer with chiral features, having the structural formula:
wherein,n=10~50;m=20~90。
preferably, the polymer with chiral features further has at least one of the following technical features:
A)、
B)、n=41;
c) M=26 or 35.
The second purpose of the invention is to provide a preparation method of the polymer with chiral characteristics, which comprises the following specific technical scheme:
a method for preparing a polymer having chiral features, comprising the steps of:
s1, mixing a macromolecular initiator, pentafluorophenol ester and azodiisobutyronitrile according to the following ratio of 1: (40-200): dissolving the molar ratio of (0.1-0.2) in dioxane, heating and stirring at 70+/-5 ℃ under the protection of dry inert gas until the reaction is finished, removing the solvent, and precipitating and purifying the reaction product in methanol to obtain a block copolymer;
s2, dissolving biphenyl liquid crystal micromolecules in dichloromethane, adding N, N-diisopropylethylamine, adding the segmented copolymer after stirring at the first normal temperature, stirring at the second normal temperature until the reaction is complete, and precipitating and purifying a reaction product to obtain the polymer with chiral characteristics.
Preferably, in the step S1, the heating and stirring time is 10-14 hours.
Preferably, in the step S2, the time of the first normal temperature stirring is 0.5-1.5 h, and the time of the second normal temperature stirring is 2-6 h.
Preferably, the reaction product is purified by precipitation in methanol 3 times to ensure complete precipitation and purification.
The third purpose of the invention is to provide a preparation method of the polymer with chiral characteristics applied to chiral cyclic nano materials, which comprises the following specific technical scheme:
the preparation method of the chiral annular nano material comprises the following steps:
and dissolving the polymer with chiral characteristics in tetrahydrofuran, adding deionized water at a specific temperature to prepare a solution, and performing circulating dialysis with molecular weight cutoff of 3500Da to obtain the chiral cyclic nanomaterial.
Preferably, the polymer with chiral features is dissolved in tetrahydrofuran and the concentration of the prepared solution is 0.1-1 wt%.
Preferably, the specific temperature is 25 to 75 ℃.
Preferably, the circulating dialysis is performed by circulating dialysis in 100mL, 500mL, 1L and 2L deionized water for several times to complete the dialysis.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for synthesizing a liquid crystal block copolymer by using an active ester polymer through a post-grafting mode, which comprises the following steps of firstly, synthesizing a polymer prepared from poly (oligoethylene glycol methacrylate) (POEGMA n ) As a macromolecular initiator, the block copolymer with the pentafluorophenol ester monomer (PFP) as a hydrophobic monomer can realize the precise control of the polymerization degree of the block copolymer; then, the biphenyl liquid crystal molecules are introduced into a block copolymer system through a grafting reaction, a series of liquid crystal block copolymers with different hydrophilic-hydrophobic ratios and different polymerization degrees are successfully synthesized, and the grafting reaction has the advantages of high grafting rate and simple and efficient synthesis process.
According to the invention, through a cyclic dialysis method, the cyclic nanomaterial with chiral characteristics is obtained by means of assembling by changing the hydrophilic-hydrophobic block proportion and the assembling temperature, the preparation and structure regulation of the chiral cyclic nanomaterial are realized, and the high controllability of the material in chiral signals is realized.
The chiral cyclic nano material prepared by the invention promotes chiral transmission and amplification of chiral primitives on the tail chain of the block copolymer through the introduction of the rigid biphenyl liquid crystal primitives, has controllable chiral signals, has wide application prospect in the field of chiral catalysts, and is beneficial to developing novel chiral catalysts with high efficiency, high selectivity and environmental friendliness.
Drawings
FIG. 1 shows a block copolymer POEGMA prepared in example 1 of the present invention 41 -b-P(NHBI-6) 26 A kind of electronic device 1 HNMR spectrogram;
FIG. 2 is a Circular Dichroism (CD) chart of the polymers with chiral characteristics prepared in the examples 1 and 2, wherein (A) is a CD spectrum of different chiral polymers and (B) is an ultraviolet absorption spectrum of different chiral polymers;
FIG. 3 is a Circular Dichroism (CD) chart of chiral cyclic nanomaterials prepared in examples 3 to 7, wherein (A) is a CD spectrum of nanomaterials at different assembly temperatures and (B) is an ultraviolet absorption spectrum of nanomaterials at different assembly temperatures;
FIG. 4 is a Circular Dichroism (CD) chart of chiral cyclic nanomaterials prepared in examples 8-12, wherein (A) is a CD spectrum of nanomaterials at different assembly temperatures and (B) is an ultraviolet absorption spectrum of nanomaterials at different assembly temperatures;
FIG. 5 is a Transmission Electron Microscope (TEM) image of the chiral cyclic nanomaterial prepared in examples 3 to 7 of the present invention, wherein (A) to (E) correspond to preparation conditions of 30, 40, 50, 60, and 70, respectively;
fig. 6 is a Transmission Electron Microscope (TEM) image of the chiral cyclic nanomaterial prepared in examples 8 to 12 of the present invention, wherein (a) to (E) correspond to preparation conditions of 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, respectively.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
For ease of understanding, the english nouns mentioned below are first explained:
POEGMA n the Chinese name of (2) is: polyethylene glycol dimethacrylate;
PFP: pentafluorophenol esters;
AIBN: azobisisobutyronitrile;
liquid nitrogen pumping and freezing: the method is a high-efficiency solvent degassing method, generally, a solution is filled into a Schlenk bottle, the solution is frozen into solid, then a vacuum pump is used for vacuumizing, then a vacuum system is closed, inert gas is filled, and the solution is slowly heated and melted.
NH 2 -Bi-2/NH 2 -Bi-4/NH 2 -Bi-6: all three are biphenyl liquid crystal small molecules;
DCM: dichloromethane;
THF: tetrahydrofuran.
Example 1:
the embodiment provides a preparation method of a polymer with chiral characteristics, which comprises the following steps:
the first step: 400mg of a macroinitiator POEGMA n Dissolving 444mg of PFP and 0.85mg of AIBN in 2mL of dioxane, performing liquid nitrogen pumping and freezing for three times, heating and stirring at 65 ℃ under the protection of dry inert gas until the reaction is finished, removing the solvent, precipitating and purifying the reaction product in methanol to obtain a segmented copolymer POEGMA n -b-PPFP m The structural formula is as follows:
where m=26, n=41.
It should be noted that, the heating and stirring time is at least 10 hours to ensure the reaction is complete, and in this embodiment, the heating and stirring time is 12 hours.
In this example, the reaction product was purified by precipitation in 40mL of methanol 3 times to ensure complete precipitation and purification.
And a second step of: 112mg of NH 2 Dissolving Bi-6 in 2mL of DCM, adding 41mg of N, N-diisopropylethylamine, stirring at normal temperature for the first time until the reaction is complete, and adding 80mg of POEGMA obtained in the first step n -b-PPFP m Stirring at normal temperature for the second time until the reaction is complete, precipitating and purifying the reaction product in methanol for 3 times to obtain pure product POEGMA n -b-P(NHBI-R1) m I.e. polymers with chiral features, also known as liquid crystalline block copolymers, of the formula:
in this embodiment:m=26, n=41, and thus, the substance can be expressed as: POEGMA (Power over coax) 41 -b-P(NHBI-6) 26 The NMR spectrum is shown in FIG. 1.
In order to make the solution more uniformly mixed, the reaction was more complete, the first stirring time at room temperature was half an hour or more, the second stirring time at room temperature was 2 hours or more, and in this example, the first stirring time at room temperature was half an hour, and the second stirring time at room temperature was 5 hours.
Example 2:
this example provides a process for preparing a polymer having chiral features, the steps being substantially identical to those of example 1, except that:
the PFP content in the first step is 595mgWhere m=35, n=41.
The second step is substantially identical.
Thus, the polymer with chiral features obtained in this example can be expressed as: POEGMA (Power over coax) 41 -b-P(NHBI-6) 35 The formulae are substantially identical to those of the corresponding polymers having chiral features in example 1, except that m=35 and n=41 in the formulae. In the preparation method of the polymer with chiral characteristics, the values of the side group structure R1 and the polymerization degrees m and n may be controlled, specifically: by replacing biphenyl liquid crystal micromolecules by NH 2 -Bi-6 substitution with NH 2 -Bi-2 or NH 2 -Bi-4, thereby modulating the R1 structure in the structural formula (respectively corresponding to ) The method comprises the steps of carrying out a first treatment on the surface of the By regulating POEGMA in the first step n The feeding ratio with PFP can obtain POEGA with different block proportions n -b-PPFP m The preferred regulatory ranges are: m=20 to 90, n=10 to 50; thereby obtaining the liquid crystal segmented copolymer POEGMA with different side group structures n -b-P(NHBI-R1) m 。
Example 3:
the embodiment provides a preparation method for applying a polymer with chiral characteristics to chiral cyclic nano materials, which specifically comprises the following steps:
the polymer with chiral characteristics is dissolved in tetrahydrofuran, the concentration of the prepared solution is 0.1-1wt%, deionized water is added at a specific temperature to prepare the solution, wherein the volume ratio of the tetrahydrofuran to the deionized water is 1:1, and the chiral cyclic nanomaterial is obtained through cyclic dialysis with the molecular weight cutoff of 3500 Da.
In this example, the polymer having chiral features was the product POEGMA prepared in example 1 41 -b-P(NHBI-6) 26 0.5mg of the product prepared in example 1 was dissolved in 1mL of tetrahydrofuran, i.e., the solution was prepared at a concentration of 0.5wt%.
In this example, the specific temperature was 30 ℃.
The dialysis was performed in a circulating manner by circulating the dialysis bag in 100mL, 500mL, 1L and 2L deionized water, respectively, to complete the dialysis.
Example 4:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 3, except that: the specific temperature was 40 ℃.
Example 5:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 3, except that: the specific temperature was 50 ℃.
Example 6:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 3, except that: the specific temperature was 60 ℃.
Example 7:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 3, except that: the specific temperature was 70 ℃.
Example 8:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 3, except that:
in this example, the polymer having chiral features was the product POEGMA prepared in example 2 41 -b-P(NHBI-6) 35 。
Example 9:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 8, except that: the specific temperature was 40 ℃.
Example 10:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 8, except that: the specific temperature was 50 ℃.
Example 11:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 8, except that: the specific temperature was 60 ℃.
Example 12:
this example provides a method for preparing a polymer with chiral features for use in chiral cyclic nanomaterial, the steps being substantially identical to those of example 8, except that: the specific temperature was 70 ℃.
The products prepared in example 1 and example 2 were each 0.5mg dissolved in 1mL THF and tested as solutions to give Circular Dichroism (CD) spectra, as shown in FIG. 2, and the prepared polymers with chiral features were found to have significant UV absorbance at 270nm and significant CD signals.
The products prepared in examples 3 to 12 were subjected to a circular dichroism spectrum (CD) test to obtain circular dichroism spectrum (CD) patterns, and as shown in fig. 3 (corresponding to examples 3 to 7) and fig. 4 (corresponding to examples 8 to 12), respectively, the prepared chiral cyclic nanomaterial was found to have significant uv absorption at 270nm and significant CD signals.
TEM tests are carried out on the products prepared in the examples 3 and 8, and the results are shown in the figures 5 and 6 respectively, and it is found that the morphology of the nanomaterial can be regulated and controlled by changing the assembly temperature and the ratio of the hydrophilic block to the hydrophobic block in the polymer, so that the chiral cyclic nanomaterial can be accurately obtained.
The embodiment of the present invention has been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiment, and various changes, modifications, substitutions, combinations, and simplifications made according to the spirit and principles of the technical scheme of the present invention can be made according to the technical principles and the inventive concept of the present invention, so long as the synthetic method of the block polymer and the preparation method and application of the polymer nanomaterial with chiral characteristics of the present invention are not deviated from the technical principles and the inventive concept of the present invention, and all belong to the protection scope of the present invention.
Claims (10)
1. A polymer having chiral features, characterized by: the structural formula of the polymer with chiral characteristics is as follows:
wherein,n=10~50;m=20~90。
2. the polymer with chiral features of claim 1, further comprising at least one of the following technical features:
A)、
B)、n=41;
c) M=26 or 35.
3. A process for preparing a polymer having chiral features, for preparing a polymer having chiral features as claimed in any one of claims 1 to 2, comprising the steps of:
s1, mixing a macromolecular initiator, pentafluorophenol ester and azodiisobutyronitrile according to the following ratio of 1: (40-200): dissolving the molar ratio of (0.1-0.2) in dioxane, heating and stirring at 70+/-5 ℃ under the protection of dry inert gas until the reaction is finished, removing the solvent, and precipitating and purifying the reaction product in methanol to obtain a block copolymer;
s2, dissolving biphenyl liquid crystal micromolecules in dichloromethane, adding N, N-diisopropylethylamine, adding the segmented copolymer after stirring at the first normal temperature, stirring at the second normal temperature until the reaction is complete, and precipitating and purifying a reaction product to obtain the polymer with chiral characteristics.
4. The method for producing a polymer having chiral characteristics according to claim 3, wherein in step S1, the heating and stirring time is 10 to 14 hours.
5. The method for preparing a polymer having chiral characteristics according to claim 3, wherein in the step S2, the first stirring time at room temperature is 0.5 to 1.5 hours and the second stirring time at room temperature is 2 to 6 hours.
6. A process for the preparation of a polymer having chiral features according to claim 3, wherein the reaction product is purified 3 times by precipitation in methanol to ensure complete precipitation purification.
7. A preparation method of chiral annular nano material is characterized in that: the polymer with chiral characteristics is dissolved in tetrahydrofuran, deionized water is added at a specific temperature to prepare a solution, and then the cyclic nanomaterial with chiral characteristics is obtained through cyclic dialysis with molecular weight cutoff of 3500Da, wherein the polymer with chiral characteristics is the polymer with chiral characteristics according to any one of claims 1 to 2.
8. The method for preparing chiral cyclic nanomaterial according to claim 7, wherein the polymer having chiral characteristics is dissolved in tetrahydrofuran and the concentration of the solution is 0.1wt% to 1wt%.
9. The method of preparing chiral cyclic nanomaterial according to claim 7, characterized in that the specific temperature is 25-75 ℃.
10. The method of claim 7, wherein the circulating dialysis comprises circulating dialysis in 100mL, 500mL, 1L and 2L deionized water for several times to complete the dialysis.
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2023
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