CN115536721B - Chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness and preparation method thereof - Google Patents
Chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness and preparation method thereof Download PDFInfo
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- 230000004043 responsiveness Effects 0.000 title claims abstract description 21
- 230000009977 dual effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 32
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
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- 238000000034 method Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- KUYMVWXKHQSIAS-UHFFFAOYSA-N tert-butyl 2-chloroacetate Chemical compound CC(C)(C)OC(=O)CCl KUYMVWXKHQSIAS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 2
- 244000038561 Modiola caroliniana Species 0.000 claims description 2
- QZHBYJZCGCZMDC-UHFFFAOYSA-N OC=1C(C2=CC3=CC=CC=C3C2=CC1O)=O Chemical compound OC=1C(C2=CC3=CC=CC=C3C2=CC1O)=O QZHBYJZCGCZMDC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910010082 LiAlH Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- -1 thioketone compound Chemical class 0.000 abstract description 36
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 230000004044 response Effects 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 230000001419 dependent effect Effects 0.000 abstract description 4
- 238000007699 photoisomerization reaction Methods 0.000 abstract description 4
- 239000004038 photonic crystal Substances 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000007779 soft material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000006399 behavior Effects 0.000 abstract 2
- 230000008859 change Effects 0.000 description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 150000001841 cholesterols Chemical class 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000001142 circular dichroism spectrum Methods 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 150000008376 fluorenones Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229910020284 Na2SO4.10H2O Inorganic materials 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- QNEPTKZEXBPDLF-JDTILAPWSA-N [(3s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] carbonochloridate Chemical compound C1C=C2C[C@@H](OC(Cl)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 QNEPTKZEXBPDLF-JDTILAPWSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- 238000006266 etherification reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness and a preparation method thereof, wherein the preparation method comprises the following steps: coupling reaction is carried out on a thioketone compound and an azide compound under the action of a catalyst to generate an optical drive chiral reversible interference spiroalkene compound with an active site, and then the interference spiroalkene compound is reacted with cholesterol or a derivative thereof to graft a cholesterol group on at least one active site of the interference spiroalkene compound. The chiral interference spiroalkene molecular motor prepared by the invention has rapid photoresponsive and temperature-dependent thermal recovery behaviors, also has temperature-dependent chiral sizes, does not influence the photoisomerization behaviors of molecules due to the existence of substituents, is expected to be applied and prepared into a new-generation multi-response material, and has wide application prospect in intelligent soft materials or responsive photonic crystals.
Description
Technical Field
The invention relates to the technical field of multi-response functional molecules and preparation thereof, in particular to a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness and a preparation method thereof.
Background
The chiral interference spirane molecular motor is proposed by the subject group of the Netherlands scientist B.L.Fernga, and derivatives with different structures are successfully synthesized, so that 2016 Nobel chemical prize is obtained. The molecules not only have the function of changing the molecular structure due to the photoinduced cis-trans isomerism of the general photoresponse molecules, but also have the function of chiral inversion which most photoresponse molecules do not have, so that the molecules are widely applied.
The chiral dynamic adjustable cholesteric liquid crystal based on the interference spiroalkene molecular motor has adjustable reflection band gap, and the gradient of light irradiation intensity in the pitch direction can be formed due to the large amount of absorption of ultraviolet light by the molecular motor, so that the pitch of the gradient is formed, and wide waves are realized. The derivative of the acrylic ester molecular motor is combined with a polymerizable liquid crystal monomer, so that intelligent soft materials such as a robot gripper, a high molecular oscillator and the like can be prepared. Therefore, the molecule has wide research and important application in the fields of intelligent soft robots, color photonic crystals or wide-wave energy-saving intelligent windows and the like.
At present, in the application of the chiral interference spiroalkene molecular motor, a molecular main body or various derivatives can only respond to light source stimulation, and only have single response performance. However, synthesis and preparation of chiral interference spiroalkene molecular motors with multiple responsivity will have wider application, but are studied.
Disclosure of Invention
Based on the above, the invention provides a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, which solves the technical problem that the existing chiral interference spiroalkene molecular motor only has single responsiveness.
In order to achieve the above purpose, the invention provides a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, and the structural general formula of the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness is shown as the following formula (1):
wherein R is 1 -R 8 Independently selected from H, or any of the formulae (2) - (11), and R 1 -R 8 Wherein at least one group selected from the group consisting of formulae (11), (2) to (11) wherein n is an integer of from 0 to 20; x is selected from any one of the formulas (12) - (15); y is 0 or 1; m is 0 or 1.
According to another aspect of the invention, the invention provides a preparation method of a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, which is characterized by comprising the following steps:
coupling reaction is carried out on a thioketone compound and an azide compound under the action of a catalyst to generate an optical drive chiral reversible interference spiroalkene compound with an active site;
reacting the interference spira compound with cholesterol or a derivative thereof to graft a cholesterol group on at least one active site of the interference spira compound;
as a further preferable embodiment of the present invention, the azide compound has any one of the following structures:
wherein R is 1 -R 8 Independently selected from H, or a group in the formulas (2) - (11), X is selected from any one of the formulas (12) - (15);
as a further preferable embodiment of the present invention, the thione compound has a structure of any one of the following:
wherein R is 1 -R 8 Independently selected from H, or a group in the formulas (2) - (11), and X is selected from any one of the groups in the formulas (12) - (15).
As a further preferable embodiment of the present invention, the cholesterol derivative has the following structure:
as a further preferable technical scheme of the invention, in the reaction of the thioketone compound and the azide compound, the reaction equivalent of the azide compound is 1 to 1.5 of that of the thioketone compound; in the reaction of grafting cholesterol groups on active sites, 1-1.2 equivalent cholesterol derivatives are added into the solution of the interference spiroalkene compound.
As a further preferable technical scheme of the invention, the thioketone compound is obtained by reacting a ketone compound with a Lawson reagent.
As a further preferable technical scheme of the invention, the ketone compound is generated by reacting naphthalene or naphthalene derivative and acrylic acid or acrylic acid derivative under the action of polyphosphoric acid, or is fluorenone or fluorenone derivative.
As a further preferable technical scheme of the invention, the azide compound is obtained by reacting a ketone compound with hydrazine hydrate and then carrying out low-temperature oxidation reaction with manganese dioxide.
The chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness can quickly generate chiral overturning under ultraviolet light irradiation, can return to an initial state by self-heating after an ultraviolet light source is removed, and has a first-order dynamics correlation relationship between the speed and the temperature of thermal recovery; by introducing cholesterol and derivatives thereof to molecular motor substituents, the cholesterol groups can be changed along with chiral inversion of photoisomerization, so that the chiral sizes of the cholesterol groups can be changed along with temperature, and the changes are sensitive. Based on the above, the chiral interference spiroalkene molecular motor provided by the invention can respond to multiple stimulus sources, so that the practical application range of the chiral interference spiroalkene molecular motor is widened.
The invention provides a preparation method of a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, which is simple to operate, and combines a cholesterol derivative with thermal responsiveness and a chiral reversible interference spiroalkene compound to prepare a bifunctional molecular motor which can generate photo-induced chiral turnover in photo-response and chiral change in thermal response; the molecular motor has thermal responsiveness to cholesterol such that the entire molecule is responsive to a thermal stimulus. Therefore, the molecule is expected to prepare a new generation of multi-response material, and has wide application prospect in intelligent soft materials or responsive photonic crystals.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an absorption spectrum curve of a chiral interference spiroalkene molecular motor of example 1 of the present invention before and after ultraviolet irradiation;
FIG. 2 is a graph showing the circular dichroism spectrum of the chiral interference spiroalkene molecular motor of example 1 of the present invention before and after ultraviolet irradiation;
fig. 3 is a graph showing the trend of the chiral spiral twisting force of the chiral interference spiroalkene molecular motor according to the embodiment 1 of the present invention with temperature.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention provides a chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, and the structural general formula of the compound is shown as the following formula (1):
wherein R is 1 -R 8 Independently selected from H, or any of the formulae (2) - (11), and R 1 -R 8 Wherein at least one group selected from the group consisting of formulae (11), (2) to (11) wherein n is an integer of from 0 to 20; x is selected from any one of the formulas (12) - (15); y is 0 or 1.
In the process of photoisomerization of the compound under the irradiation of ultraviolet light, the chiral size of molecules changes, and finally the compound turns over and can spontaneously return to an initial thermal stable state after the excitation is stopped. Meanwhile, the molecule has a thermally responsive cholesterol substituent, the chiral size of the cholesterol molecule can change obviously with temperature, so that the chiral size of the cholesterol grafted molecule motor can be regulated by ultraviolet irradiation and even chiral turnover occurs, and the chiral property of the cholesterol grafted molecule motor can also change with temperature. The compound has rapid photoresponsivity and temperature-dependent thermal recovery behavior, also has temperature-dependent chiral size, does not influence the isomerization behavior of light of molecules due to the existence of substituent groups, and has wide application prospect.
The preparation method of the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness comprises the following steps:
according to the reaction equivalent of the azide compound being 1-1.5 of the thioketone compound, the thioketone compound and the azide compound are subjected to coupling reaction under the action of a catalyst to generate an optical drive chiral reversible interference spiroalkene compound with an active site; then adding 1-1.2 equivalents of cholesterol or derivatives thereof into the solution of the interference spirane compound, and grafting cholesterol groups on the active site of the interference spirane compound through esterification and/or etherification reaction.
The azide compound has a structure of any one of the following:
wherein R is 1 -R 8 Independently selected from H, or a group in the formulas (2) - (11), and X is selected from any one of the groups in the formulas (12) - (15).
The thioketone compound has a structure of any one of the following:
wherein R is 1 -R 8 Independently selected from H, or a group in the formulas (2) - (11), and X is selected from any one of the groups in the formulas (12) - (15).
The cholesterol derivative has the following structure:
specifically, the coupling reaction of the thioketone compound and the azide compound is carried out, and the specific method for generating the light-driven chiral reversible interference spiroalkene compound with an active site is as follows:
dissolving a thioketone compound in a toluene solution, adding 1-1.2 equivalent of an azide compound, stirring for half an hour at room temperature, adding triphenylphosphine, stirring for 0.5h at room temperature, heating to 90 ℃ for reaction for 36h until the reactants are completely or completely decomposed, performing rotary evaporation, dissolving the concentrate in an diethyl ether solvent, adding methyl iodide for reaction for 24h at room temperature, removing excessive triphenylphosphine, after the reaction is finished, removing insoluble solids by suction filtration, removing the solvent by reduced pressure distillation, and purifying by column chromatography to obtain the light-driven chiral reversible interference spiroalkene compound with an active site.
Specifically, the grafting of cholesterol can be directly obtained by reacting a cholesterol derivative with an optical drive chiral reversible interference spiroalkene compound with an active site under the action of a catalyst, and the specific method is as follows:
dissolving chiral interference spiroalkene molecular motor with active site in dichloromethane solution, adding dicyclohexylcarbodiimide, 4-dimethylaminopyridine and other catalyst, magnetically stirring at room temperature, adding 1-1.5 equivalents of cholesterol derivative, reacting at room temperature until the reaction is completed, freezing to remove insoluble matter, vacuum rotary steaming, and purifying the concentrate by column chromatography.
In one example, the thioketone compound of the present invention can be obtained by reacting a ketone compound with a lawsen reagent, which is specifically implemented as follows:
dissolving ketone compounds in toluene solvent, heating to 90 ℃ and magnetically stirring, then adding 1-1.2 equivalents of Lawson reagent, gradually changing the solvent in the reaction process into blue or purple, reacting for 10 hours till the reaction is finished, performing rotary evaporation under reduced pressure, and purifying the concentrate by using a column chromatography method to obtain the thioketone compound. It should be noted that the thioketone compound is extremely unstable and is extremely easily decomposed, and thus it is required to be immediately put into the next reaction.
In another example, the ketone compound in the present invention may be generated by reacting naphthalene or a naphthalene derivative with acrylic acid or an acrylic acid derivative under the action of polyphosphoric acid, or the ketone compound may be directly selected as fluorenone or a fluorenone derivative. Wherein the reaction of naphthalene or its derivatives with acrylic acid or its derivatives in polyphosphoric acid is carried out as follows:
mixing naphthalene or its derivative with polyphosphoric acid, placing in a reaction container, heating to 50deg.C, mechanically stirring, stirring for a period of time, sequentially adding 3-6 equivalents of acrylic acid or its derivative, heating to 70deg.C, stirring for 5 hr, repeatedly extracting with saturated sodium bicarbonate solution, saturated saline, deionized water, etc., purifying the product by column chromatography silica gel method, and collecting the final product as pale yellow solid powder or white solid powder.
In one example, the azide compound of the present invention is obtained by reacting a ketone compound with hydrazine hydrate and then subjecting the resultant product to a low-temperature oxidation reaction with manganese dioxide, and the specific implementation thereof is as follows:
dissolving a ketone compound in a certain amount of ethanol, heating to 80 ℃ for reflux, magnetically stirring, adding 1-1.5 equivalents of hydrazine hydrate, cooling the reactant to room temperature after the reaction is finished, cooling, purifying the product by using a recrystallization method, wherein the reactant is in a yellow needle crystal or yellow oily liquid; the reactant is added into dichloromethane solution, 5 equivalents of manganese dioxide powder is added during the reaction temperature is controlled to be between-5 and 0 ℃, the reaction is carried out for 7 hours until the reaction is finished, vacuum decompression and suction filtration are carried out, filtrate is taken, and the product is purified by column chromatography. Azide compounds are likely to decompose and produce byproducts at high temperatures, and therefore should be stored in a refrigerated environment at about-20 ℃.
Potential applications of the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness provided by the invention include, but are not limited to:
1) Based on the chiral size change and the turning characteristic of molecules, the method can be applied to the fields of cholesteric liquid crystal reflection band gap change, photoinduced structural color change, broadband reflection and optical writing liquid crystal display;
2) Based on the photo-thermal response characteristic of the molecular motor, the molecular motor is combined with a polymerizable liquid crystal monomer to prepare a color photonic crystal film which is used in the fields of color photonic labels, anti-counterfeiting labels and the like
3) The preparation of the cholesteric coating based on the photoisomerization property of the molecules realizes the overturning of the molecular motor by using a light or heat stimulus source, thereby driving the rotary motion of objects such as micro glass rods and the like.
In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the technical solution of the present invention will be further described in detail below through specific embodiments.
Example 1:
chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness, R is used for 8 The structure is cholesterol group, R 1 -R 7 The structure is H, X is methyl, m is 0, y is 0, and the molecular structure is specifically shown as follows:
the synthesis method of the compound comprises the following steps:
step 1, dissolving 10g of monomethoxy naphthalene in 200ml of polyphosphoric acid, placing the polyphosphoric acid in a flask, heating to 50 ℃, mechanically stirring, sequentially adding 10g of methacrylic acid, mechanically stirring for reaction for 8 hours, cooling the reaction liquid to room temperature by ice cubes, extracting by dichloromethane, respectively washing twice by saturated sodium bicarbonate aqueous solution and deionized water, separating the aqueous layer, absorbing residual water by anhydrous magnesium sulfate, purifying by a column after removing the solvent by reduced pressure distillation, removing the solvent by reduced pressure rotary evaporation to obtain 7.2g of white powder, wherein the yield is 67%.
Step 2, the product from step 1 (5 g,22.095 mol) was dissolved in toluene solvent, heated to 90 ℃, alCl3 (4.4 g,22 mmol) was added, the reaction was continued for five hours, water was added to the reaction mass, extraction was performed with ethyl acetate, the organic layer was washed three times with 0.5M hydrochloric acid solution and aqueous solution, and then the solution was dried over anhydrous magnesium sulfate. The solvent is removed by rotary evaporation, the crude product is purified by column chromatography silica gel method, petroleum ether: ethyl acetate = 2:1, orange hot solids (1.2 g,51% yield) were produced.
Step 3, dissolving the product (2 g,9.45 mmol) of step 2 and K2CO3 (1.46 g,10.5 mmol) in N, N dimethylformamide, heating to 50 ℃, adding tert-butyl chloroacetate, then heating to 80 ℃ for reaction for 5 hours, cooling the reaction solution to room temperature, then steaming, extracting a crude product, and purifying by column chromatography, petroleum ether: the ethyl acetate ratio is 5:2 as yellow solid (3.1 g, 82%).
Step 4, dissolving the product (50 mg,0.15 mmol) of the step 3 in tetrahydrofuran solvent, adding Lawson reagent, heating the reactant to 50 ℃ for reaction for 5 hours, rotary evaporation, taking a crude product, purifying by a column chromatography silica gel method, and petroleum ether: ethyl acetate = 10:1, the product was a purple solid (40 mg, 78%).
Step 5, dissolving the product (540 mg,1.58 mmol) of step 4 in toluene solution, adding azide and triphenylphosphine, stirring the solvent for 3h at room temperature, heating to reflux for 13h, decompressing, steaming the reaction intermediate, redissolving the reaction intermediate in diethyl ether solvent (25 ml), adding methyl iodide (0.3 ml) and stirring the reaction product for 12h at room temperature to generate white precipitate, carrying out suction filtration, rotary steaming concentration on the reactant, purifying the crude product by column chromatography, wherein the leaching agent ratio is petroleum ether: ethyl acetate = 2:1, the product was a yellow solid with a yield of 52%.
Step 6, the product (1 g,2 mmol) of step 5 is dissolved in tetrahydrofuran solvent, the reaction device is placed in an ice-water bath, liAlH4 (700 mg,18.4 mmol) is slowly added, stirring is carried out at 0 ℃ for 5h, and after the reaction is finished, the reaction solution is quenched with excessive Na2SO4.10H 2O. Then the reactant is placed at room temperature, the solid is removed by suction filtration, the reactant is repeatedly washed by ethyl acetate solvent for several times, the filtrate is taken out, the filtrate is decompressed and distilled in a rotary way, the obtained concentrate is purified by a column chromatography method, and the leaching agent proportion is petroleum ether: ethyl acetate = 2:1, the product was a yellow solid with a yield of 58.8%.
Step 7, dissolving the product (0.5 g,1.24 mmol) of step 6, pyridine (0.22 mL,2.5 mmol), dimethylaminopyridine (14 mg) and cholesterol chloroformate (0.6 g,1.36 mmol) in a dry dichloromethane solution, magnetically stirring, reacting for 48h, washing the reaction solution with saturated saline and deionized water for three times, finally drying with anhydrous magnesium sulfate, filtering under reduced pressure, distilling to obtain a concentrate, purifying the crude product by a column chromatography method, wherein the proportion of the eluent is petroleum ether: ethyl acetate = 5:1, the final product was a yellow solid with 54% yield.
Testing the product obtained in the step 7, and testing the changes of the ultraviolet absorption spectrum and the circular dichroism spectrum before and after ultraviolet irradiation, as shown in figures 1 and 2, so as to characterize the photoresponsive performance and chiral inversion; meanwhile, a polarizing microscope is used for testing the change rule of the thread pitch along with the temperature in the wedge box, as shown in fig. 3, the space between the stripes is gradually reduced along with the temperature rise, and the corresponding spiral twisting force is increased, so that the change of chirality along with the temperature is shown.
Example 2:
the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness takes R1, R6 and R8 structures as cholesterol formyl chloride groups, the rest group structures are H, X is methyl, m is 0, y is 0, and the specific molecular structure is as follows:
the synthesis method of the compound comprises the following steps:
step 1, dihydroxyfluorenone (10 g) and K2CO3 (5.3 g) are dissolved in N, N dimethylformamide, tert-butyl chloroacetate (8 g) is added after heating to 50 ℃, then the temperature is raised to 80 ℃ for reaction for 8 hours, the reaction liquid is cooled to room temperature, solid insoluble salt substances are removed by suction filtration, the filtrate is distilled to extract a crude product, ethanol is used for recrystallization, and the product is yellow solid (8 g, the yield is 82%).
Step 2, dissolving the product in the step 1 in a mixed solvent of 300ml of hydrazine hydrate and 50ml of ethanol, adding 0.5ml of acetic acid, stirring and reacting for 8 hours, dissolving the recrystallized solid in dichloromethane, adding 7.06g of manganese dioxide, stirring in an ice water bath for 8 hours, filtering the obtained product to remove the solid, distilling the filtrate under reduced pressure to remove the solvent, purifying by a column, wherein the eluent is a mixed solvent of petroleum ether and triethylamine in a ratio of 20:1, and drying to obtain 3g of warm orange solid with a yield of 52%; and (5) putting the product into a refrigerator at the temperature of minus 20 ℃ for refrigeration.
And 3, dissolving 8g of monomethoxy naphthalene in 150ml of polyphosphoric acid, placing the polyphosphoric acid in a flask, heating to 80 ℃, mechanically stirring, sequentially adding 6g of methacrylic acid, mechanically stirring for reaction for 5 hours, cooling the reaction liquid to room temperature by ice cubes, extracting by using dichloromethane, respectively washing twice by using saturated sodium bicarbonate aqueous solution and deionized water, separating the aqueous layer, absorbing residual water by using anhydrous magnesium sulfate, distilling under reduced pressure to remove the solvent, purifying by column chromatography, removing the solvent by using a mixed solvent of ethyl acetate and petroleum ether 1:5, and performing rotary evaporation under reduced pressure to obtain white powder 5.6g with the yield of 67%.
Step 4, dissolving the product (1 g) in the step 3 in toluene solvent, heating to 90 ℃, adding AlCl3 (2 g) for continuous reaction for five hours, adding water into the reactant, extracting with ethyl acetate, washing the organic layer three times with 0.5M hydrochloric acid solution and aqueous solution, and then drying the solution with anhydrous magnesium sulfate. The solvent is removed by rotary evaporation, the crude product is purified by column chromatography silica gel method, petroleum ether: ethyl acetate = 2:1, orange hot solids (0.5 g, 50% yield) were produced.
Step 5, dissolving the product (2 g,9.45 mmol) of step 4 and K2CO3 (1.46 g,10.5 mmol) in N, N dimethylformamide, heating to 50 ℃, adding tert-butyl chloroacetate, then heating to 80 ℃ for reaction for 5 hours, cooling the reaction solution to room temperature, extracting the crude product by rotary evaporation, purifying by column chromatography, and petroleum ether: the ethyl acetate ratio is 5:2 as yellow solid (3.1 g, 82%).
Step 6, dissolving the product (1 g) in the step 5 in tetrahydrofuran solvent, adding 1.2 equivalents of Lawson reagent, heating the reactant to 60 ℃ for reaction for 4.5 hours, performing rotary evaporation to obtain a crude product, purifying by a column chromatography silica gel method, and mixing the petroleum ether with the leaching agent in the ratio of: ethyl acetate = 10:1, the product was a mauve solid (60 mg, 78%).
Step 7, 1.64g of the product of the step 2 and 1.89g of the product of the step 6 are dissolved in 100ml of toluene solution, triphenylphosphine is added after stirring for one hour at room temperature, the mixture is reacted for 3 hours at room temperature, then an oil bath is heated to be heated to 90 ℃ until the reaction is finished for 8 hours, solids are removed by filtration, the filtrate is distilled under reduced pressure to remove the solvent, and then the solvent is purified by column chromatography, wherein the leaching agent is ethyl acetate and petroleum ether 5:1 to give, after drying, 0.5g of a yellow solid in 31.2% yield.
Step 8, dissolving the product (0.5 g) obtained in the step 7 into tetrahydrofuran solvent, controlling the reaction temperature to be 0 ℃, slowly adding nine times equivalent of LiAlH4 (2 g), controlling the solution to be stirred in ice water bath for 5 hours, and quenching the reaction solution with excessive Na2SO4.10H2O after the reaction is finished; then the reactant is placed at room temperature, the solid is removed by suction filtration, the reactant is repeatedly washed by ethyl acetate solvent for several times, the concentrated solution obtained by decompression and rotary evaporation of the filtrate is purified by column chromatography, and the leaching agent proportion is methanol: ethyl acetate = 1:20 as yellow solid with a yield of 78.8%.
Step 9, dissolving the product (0.5 g), dicyclohexylcarbodiimide (0.3 g), dimethylaminopyridine (14 mg) and cholesterol formic acid (0.75 g) in a dried dichloromethane solution, magnetically stirring, reacting for 36h, and after the reaction is finished, performing vacuum filtration and distillation on the reaction solution to obtain a concentrate, wherein the crude product is purified by a column chromatography method, and the proportion of the eluent is petroleum ether: ethyl acetate = 5:1, the final product was a yellow solid with a yield of 20.1%.
The method adopts the mode of connecting the same substituent groups to the rotor and stator parts of the molecular motor, can use the same type of reaction, adopts a one-step synthesis method to connect cholesterol substituent groups to three active sites, and is convenient to synthesize. The product of the step 9 is characterized, the change of the ultraviolet absorption spectrum and the circular dichroism spectrum before and after ultraviolet irradiation is observed, the change of the spectrum similar to that of the embodiment 1 can be observed, the red shift of the absorption spectrum and the slight decrease of the absorption intensity are observed, the red shift of the peak of the circular dichroism spectrum and the switching of the positive and negative directions of the peak prove that the chiral of the molecule is overturned; meanwhile, the variation of the fringe spacing along with the temperature in the wedge box is observed by using a polarizing microscope, and the experimental phenomenon that the fringe spacing is obviously reduced along with the temperature rise is provided, so that the molecule has excellent thermal response performance.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (2)
1. The chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness is characterized by comprising the following structural formula:
。
2. a method for preparing the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness as claimed in claim 1, comprising the following steps:
step 1, dihydroxyfluorenone 10g and K 2 CO 3 5.3g is dissolved in N, N dimethylformamide, after heating to 50 ℃, 8g tert-butyl chloroacetate is added, then the temperature is raised to 80 ℃ for reaction for 8 hours, the reaction liquid is cooled to room temperature, solid insoluble salt substances are removed by suction filtration, the filtrate is distilled and crude products are extracted by ethanol, and the products are recrystallized to obtain yellow solids;
step 2, dissolving the product in the step 1 in a mixed solvent of 300ml hydrazine hydrate and 50ml ethanol, adding 0.5ml acetic acid, stirring for reacting 8h, dissolving the recrystallized solid in dichloromethane, adding 7.06g manganese dioxide, stirring 8h in an ice water bath, filtering the obtained product to remove the solid, distilling the filtrate under reduced pressure to remove the solvent, purifying by column chromatography, wherein the eluent is a mixed solvent of petroleum ether and triethylamine 20:1, and drying to obtain a warm orange solid;
step 3, dissolving monomethoxy naphthalene 8g in 150ml polyphosphoric acid, heating to 80 ℃, mechanically stirring, sequentially adding 6g methacrylic acid, mechanically stirring for reacting 5h, cooling the reaction liquid to room temperature, extracting with dichloromethane, washing with saturated sodium bicarbonate aqueous solution and deionized water twice, separating to remove water layer, absorbing residual water with anhydrous magnesium sulfate, distilling under reduced pressure to remove solvent, purifying by column chromatography, eluting with mixed solvent of ethyl acetate and petroleum ether 1:5, and distilling under reduced pressure to remove solvent to obtain white powder;
step 4, step 3The product 1g in (2) is dissolved in toluene solvent, heated to 90 ℃, and added with 2g of AlCl 3 The reaction was continued for five hours, water was added to the reaction mass, extraction was performed with ethyl acetate, the organic layer was washed with 0.5. 0.5M hydrochloric acid solution and aqueous solution, then the solution was dried over anhydrous magnesium sulfate, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography silica gel method, eluting with petroleum ether and ethyl acetate 2:1 to produce orange hot solid;
step 5, combining the product of step 4, 2g,9.45mmol, and K of 1.46g,10.5mmol 2 CO 3 Dissolving in N, N dimethylformamide, heating to 50 ℃, adding tert-butyl chloroacetate, then heating to 80 ℃ for reaction for 5 hours, cooling the reaction liquid to room temperature, extracting a crude product by rotary evaporation, purifying by a column chromatography, wherein the eluent is petroleum ether and ethyl acetate 5:2, the product is yellow solid;
step 6, dissolving the product 1g in the step 5 in tetrahydrofuran solvent, adding 1.2 equivalents of Lawson reagent, heating the reactant to 60 ℃ to react 4.5h, performing rotary evaporation to obtain a crude product, purifying by a column chromatography silica gel method, and mixing petroleum ether and ethyl acetate 10 in the ratio of the leaching agent: 1, and the product is a mauve solid;
step 7, dissolving the product 1.64g of the step 2 and the product 1.89g of the step 6 in 100ml toluene solution, stirring at room temperature for dissolution, adding triphenylphosphine, reacting at room temperature for 3 hours, heating in an oil bath to 90 ℃ until the reaction is finished by 8h, filtering to remove solids, distilling the filtrate under reduced pressure to remove the solvent, purifying by a column, and eluting with ethyl acetate and petroleum ether 5:1, and drying to obtain yellow solid;
step 8, dissolving the product 0.5. 0.5g of the step 7 in tetrahydrofuran solvent, controlling the reaction temperature to be 0 ℃, and slowly adding nine times of equivalent LiAlH 4 Stirring in ice water bath for 5 hr, and adding excessive Na 2 SO 4 .10H 2 Quenching by O; the reaction is then left at room temperature, the solids are removed by suction filtration, the mixture is repeatedly rinsed with ethyl acetate solvent, the filtrate is concentrated by rotary evaporation under reduced pressure, the concentrate is purified by column chromatography, and the leaching agent is usedMethanol and ethyl acetate 1:20, the product is a yellow solid;
step 9, dissolving the product 0.5g, dicyclohexylcarbodiimide 0.3g, dimethylaminopyridine 14mg and cholesterol formic acid 0.75g in a dried dichloromethane solution, magnetically stirring, reacting 36h, decompressing, filtering and distilling the reaction solution to obtain a concentrate after the reaction, purifying the crude product by a column chromatography method, wherein the eluent is petroleum ether and ethyl acetate 5:1, and the final product is yellow solid, namely the chiral interference spiroalkene molecular motor with photo-thermal dual responsiveness.
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| CN109270712A (en) * | 2018-09-19 | 2019-01-25 | 北京化工大学 | A kind of liquid crystal film and its preparation method and application |
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| CN109776719A (en) * | 2017-11-13 | 2019-05-21 | 北京大学 | A kind of preparation method, macromolecule membrane and the device of the photo-deformable liquid crystal polymer film based on helicene class molecule |
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| CN101544895A (en) * | 2009-05-08 | 2009-09-30 | 北京科技大学 | Method for preparing chiral nematic liquid crystal material |
| CN102643432A (en) * | 2012-04-01 | 2012-08-22 | 北京科技大学 | Preparation method for cholesteric siloxane side-chain liquid crystal polymer |
| CN109776329A (en) * | 2017-11-13 | 2019-05-21 | 北京大学 | It is a kind of can photic chiral overturning multicomponent methacrylate class compound, preparation method and device |
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