CN114471706A - Preparation method of organic framework nanofiber tube - Google Patents
Preparation method of organic framework nanofiber tube Download PDFInfo
- Publication number
- CN114471706A CN114471706A CN202210161339.4A CN202210161339A CN114471706A CN 114471706 A CN114471706 A CN 114471706A CN 202210161339 A CN202210161339 A CN 202210161339A CN 114471706 A CN114471706 A CN 114471706A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- tube
- nanofiber tube
- framework nanofiber
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 39
- 239000013384 organic framework Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 108010024636 Glutathione Proteins 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HAXFWIACAGNFHA-UHFFFAOYSA-N aldrithiol Chemical compound C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 claims description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 13
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001338 self-assembly Methods 0.000 claims description 10
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CYWHLOXWVAWMFO-UHFFFAOYSA-N 3-sulfanyl-1h-pyridine-2-thione Chemical compound SC1=CC=CN=C1S CYWHLOXWVAWMFO-UHFFFAOYSA-N 0.000 claims description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 claims description 7
- 229940014800 succinic anhydride Drugs 0.000 claims description 7
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 6
- PORTXTUJPQINJC-UHFFFAOYSA-N 2-(pyridin-2-yldisulfanyl)ethanol Chemical compound OCCSSC1=CC=CC=N1 PORTXTUJPQINJC-UHFFFAOYSA-N 0.000 claims description 5
- -1 hydroxyethyl dipyridyl disulfide Chemical compound 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229940043348 myristyl alcohol Drugs 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940057402 undecyl alcohol Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract 2
- 230000032050 esterification Effects 0.000 abstract 1
- 229960003180 glutathione Drugs 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/40—
-
- B01J35/58—
-
- B01J35/617—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/02—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link
- C07K5/0215—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link containing natural amino acids, forming a peptide bond via their side chain functional group, e.g. epsilon-Lys, gamma-Glu
Abstract
The invention discloses a preparation method of an organic framework nanofiber tube, and belongs to the technical field of preparation and application of nanomaterials. The invention prepares the amphiphilic biological supermolecule by ring opening, esterification, substitution reaction and the like, wherein an aliphatic alcohol fatty chain is used as a hydrophobic part, glutathione is used as a hydrophilic part, the hydrophilic and hydrophobic parts are connected by a disulfide bond, and the amphiphilic biological supermolecule with proper concentration can be self-assembled into a hollow structure nano-fiber tube by controlling ultrasonic power and time in selective solvent water. The nano-fiber tube prepared by the method has the advantages of uniform size distribution, large specific surface area, high porosity and many active sites, and the method has the advantages of simple technical route, easy control, low cost of raw materials, wide sources and suitability for large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation and application of nano materials, in particular to a preparation method of an organic framework nanofiber tube.
Background
The nano material is a particle with the size of about 1-100 nm, is a typical mesoscopic system, has the surface effect, the small-size effect and the macroscopic quantum tunneling effect, and has the remarkable characteristics different from the macroscopic material in the aspects of photoelectric, magnetic, mechanical and chemical reactions. The nano materials can be roughly classified into four types, namely nano powder, nano fiber, nano film, nano particle and the like. The nanofiber tube is a nanofiber material with a hollow structure, belongs to nanofibers, has a large specific surface area and a large number of active sites, and is greatly concerned by researchers. The nanometer material has wide application range, such as nanometer electronic device, nanometer medical treatment, nanometer biotechnology, environment, energy source, etc. The wide application scenes put higher requirements on the nano materials, for example, the preparation of the nano materials tends to be multifunctional, and the like. The preparation method is mainly used for synthesizing various oxide nano materials by a hydrothermal method, a hard template method and an electrostatic spinning method. However, the specific surface area and active sites of the nano-material prepared by the preparation method in the prior art cannot be obviously improved, and the wide application of the nano-material is severely limited.
Disclosure of Invention
The invention aims to provide a preparation method of an organic framework nanofiber tube.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: a preparation method of an organic framework nanofiber tube comprises the following steps:
(1) carrying out ring-opening addition reaction on fatty alcohol and succinic anhydride to prepare saturated fatty acid;
(2) carrying out disulfide bond exchange reaction on mercaptoethanol and dipyridyl disulfide to prepare hydroxyethyl dipyridyl disulfide;
(3) mixing saturated fatty acid and hydroxyethyl dithiopyridine, and carrying out esterification reaction under the action of a catalyst to obtain a saturated fatty chain with the tail end connected with the dithiopyridine;
(4) preparing an amphiphilic biological supermolecule by carrying out a disulfide bond exchange reaction on a saturated fatty chain with the tail end connected with dithiopyridine and reduced glutathione;
(5) self-assembling by taking amphiphilic biological supermolecules as a raw material to prepare the organic framework nano fiber tube;
the structural general formula of the amphiphilic biomolecule of the organic framework nanofiber tube is shown as the formula (1):
wherein n is greater than 0.
Further, the number of carbon atoms of the fatty alcohol in the step (1) is more than 0.
Further, the fatty alcohol includes myristyl alcohol, undecyl alcohol, arachidyl alcohol, and the like.
Further, the molar ratio of the fatty alcohol to the succinic anhydride in the step (1) is 1:1.
Further, the molar ratio of mercaptoethanol to dithiodipyridine in the step (2) is 1: 1.2-1: 3.
Further, the molar ratio of the saturated fatty acid to the hydroxyethyl dipyridyl disulfide in the step (3) is 1: 1-1: 2; the catalyst is 4-Dimethylaminopyridine (DMAP).
Further, the molar ratio of the saturated fatty chain of the end-linked dithiopyridine and the reduced glutathione in the step (4) is 1:1.
Further, the self-assembly of step (5) specifically includes: self-assembly is carried out under the ultrasonic condition; the ultrasonic power is 50-100 Hz, the temperature is 25-30 ℃, and the time is 30-120 min.
The second technical scheme of the invention is as follows: the organic framework nanofiber tube prepared by the preparation method of the organic framework nanofiber tube.
The third technical scheme of the invention is as follows: the application of the organic framework nanofiber tube in the fields of catalysis, separation and sensing.
The invention discloses the following technical effects:
(1) the invention prepares amphiphilic biological supermolecule for the first time, and the supermolecule is placed in water for ultrasonic self-assembly to prepare the organic framework nano-fiber tube.
(2) The nano fiber tube prepared by ultrasonic self-assembly has application prospect in the fields of catalysis, separation, sensing and the like.
(3) The invention has the advantages of cheap and easily obtained raw materials, easy operation of the self-assembly process and suitability for mass production of enterprises.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a diagram of the ultrasonic dispersion of amphiphilic biomolecular molecules prepared in example 1 of the present invention in selected solvent water;
FIG. 2 is a transmission electron microscope image of an organic framework nanofiber tube prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic spectrum of an intermediate compound of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and materials in connection with which they pertain. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
A preparation method of an organic framework nanofiber tube comprises the following steps:
(1) preparation of intermediate 2 a: 2.14g (10mmol) of myristyl alcohol (1a) and 100mL of anhydrous dichloromethane are added into a 200mL round bottom flask to be dissolved, 1.21g (12mmol) of anhydrous triethylamine is added, the mixture is stirred uniformly, 1g (10mmol) of succinic anhydride is added, the mixture is stirred at room temperature and reacted for 12 hours, after the reaction is completed, the mixture is washed by dilute hydrochloric acid solution, saturated sodium bicarbonate solution and water in sequence, finally the mixture is dried by anhydrous sodium sulfate, suction filtration and spin drying are carried out, and chromatographic column separation is carried out, so that 2.7g of saturated fatty acid (white powder, 2a) is obtained, and the yield is 86%.
(2) Preparation of intermediate 3 a: 2.2g (10mmol) of dithiodipyridine and 40mL of methanol were added to a 200mL round-bottomed flask to dissolve the dithiodipyridine solution, then 0.78g (10mmol) of mercaptoethanol was dissolved in 20mL of methanol to obtain a mercaptoethanol solution, the mercaptoethanol solution was placed in a constant pressure dropping funnel, slowly added dropwise to the dithiodipyridine solution, the dropwise addition was completed, the mixture was stirred overnight at room temperature, after the reaction was completed, the methanol was dried by spinning, and the mixture was purified by column chromatography to obtain 1.67g of hydroxyethyl dithiopyridine (pale yellow semisolid, 3a) with a yield of 89%.
(3) Preparation of intermediate 4 a: 2g (6.14mmol) of the intermediate 2a is dissolved in anhydrous dichloromethane, 1.38g (7.27mmol) of the intermediate 3a is added and dissolved by stirring, 1.52g (7.37mmol) of dicyclohexylcarbodiimide (dehydrating agent, DCC) and 0.9g (7.37mmol) of DMAP (catalyst) are added and dissolved, the mixture is stirred at room temperature overnight, after the reaction is finished, diluted hydrochloric acid solution, saturated sodium bicarbonate solution and water are used for washing in sequence, finally anhydrous sodium sulfate is used for drying, suction filtration and spin drying are carried out, chromatographic column separation is carried out, 2.3g of saturated aliphatic chain (pale yellow solid, 4a) with the end connected with dithiopyridine is obtained, and the yield is 77%.
(4) Preparation of intermediate 5 a: dissolving 4.83g (10mmol) of the intermediate 4a in 20mL of DMF to obtain a DMF solution of the intermediate 4a, then dissolving 3.65g (10mmol) of reduced glutathione in 10mL of water to obtain a reduced glutathione aqueous solution, adding the reduced glutathione aqueous solution into the DMF solution, stirring overnight until the system turns yellow, placing the system in a dialysis bag, removing the DMF in the system, and precipitating 5.7g of white solid, namely the amphiphilic biological supramolecule (5a), wherein the yield is 85%.
(5) Preparing an organic framework nanofiber tube: and (2) placing 5mg of 5a in 5mL of deionized water, carrying out ultrasonic self-assembly at the ultrasonic frequency of 100Hz and the temperature of 25 ℃ for 20min, then adjusting the ultrasonic frequency to 50Hz, continuing ultrasonic treatment for 120min, and standing to obtain the organic framework nanofiber tube.
The reaction process is as follows:
example 2
(1) Preparation of intermediate 2 b: 1.72g (10mmol) of undecanol (1b) and 100mL of anhydrous dichloromethane are added into a 200mL round-bottom flask, after dissolving, 1.21g (12mmol) of anhydrous triethylamine is added, the mixture is stirred uniformly, 1g (10mmol) of succinic anhydride is added, the mixture is stirred at room temperature and reacted for 12 hours, after the reaction is finished, diluted hydrochloric acid solution, saturated sodium bicarbonate solution and water are sequentially used for washing, finally, the mixture is dried by anhydrous sodium sulfate, suction filtration and spin drying are carried out, and chromatographic column separation is carried out, so that 2.3g of saturated fatty acid (white powder, 2b) is obtained, and the yield is 85%.
(2) Preparation of intermediate 3 a: 2.2g (10mmol) of dithiodipyridine and 40mL of methanol were added to a 200mL round-bottomed flask to dissolve the dithiodipyridine solution, then 0.78g (10mmol) of mercaptoethanol was dissolved in 20mL of methanol to obtain a mercaptoethanol solution, the mercaptoethanol solution was placed in a constant pressure dropping funnel, slowly added dropwise to the dithiodipyridine solution, the dropwise addition was completed, the mixture was stirred overnight at room temperature, after the reaction was completed, the methanol was dried by spinning, and the mixture was purified by column chromatography to obtain 1.67g of hydroxyethyl dithiopyridine (pale yellow semisolid, 3a) with a yield of 89%.
(3) Preparation of intermediate 4 b: 1.67g (6.14mmol) of intermediate 2b was dissolved in anhydrous dichloromethane, 1.38g (7.27mmol) of intermediate 3a was added and dissolved by stirring, 1.52g (7.37mmol) of DCC (dehydrating agent) and 0.9g (7.37mmol) of DMAP (catalyst) were added and dissolved, and the mixture was stirred at room temperature overnight, after completion of the reaction, the mixture was washed with dilute hydrochloric acid solution, saturated sodium bicarbonate solution and water in this order, and finally dried over anhydrous sodium sulfate, followed by suction filtration and spin drying, and column chromatography separation to obtain 2.1g of a dithiopyridine-terminally linked saturated aliphatic chain (pale yellow solid, 4b) in 77% yield.
(4) Preparation of intermediate 5 b: dissolving 4.41g (10mmol) of the intermediate 4b in 20mL of DMF to obtain a DMF solution of the intermediate 4b, then dissolving 3.65g (10mmol) of reduced glutathione in 10mL of water to obtain a reduced glutathione aqueous solution, adding the reduced glutathione aqueous solution into the DMF solution, stirring overnight until the system turns yellow, placing the system in a dialysis bag, removing the DMF in the system, and precipitating 5.5g of white solid, namely the amphiphilic biological supramolecule (5b), wherein the yield is 85%.
(5) Preparing an organic framework nanofiber tube: and (3) placing 5mg of 5b in 5mL of deionized water, carrying out ultrasonic self-assembly at the ultrasonic frequency of 100Hz and the temperature of 25 ℃ for 20min, then adjusting the ultrasonic frequency to 50Hz, continuing ultrasonic treatment for 90min, and standing to obtain the organic framework nanofiber tube.
The reaction process is as follows:
example 3
(1) Preparation of intermediate 2 c: 2.98g (10mmol) of arachidyl alcohol (1c) and 100mL of anhydrous dichloromethane are added into a 200mL round-bottom flask to be dissolved, 1.21g (12mmol) of anhydrous triethylamine is added, the mixture is stirred uniformly, 1.2g (12mmol) of succinic anhydride is added, the mixture is stirred at room temperature and reacts for 12 hours, after the reaction is completed, diluted hydrochloric acid solution, saturated sodium bicarbonate solution and water are sequentially used for washing, finally, anhydrous sodium sulfate is used for drying, suction filtration and spin drying are carried out, chromatographic column separation is carried out, 3.2g of saturated fatty acid (white powder, 2c) is obtained, and the yield is 80%.
(2) Preparation of intermediate 3 a: 2.2g (10mmol) of dithiodipyridine and 40mL of methanol were added to a 200mL round-bottomed flask to dissolve the dithiodipyridine solution, then 0.78g (10mmol) of mercaptoethanol was dissolved in 20mL of methanol to obtain a mercaptoethanol solution, the mercaptoethanol solution was placed in a constant pressure dropping funnel, slowly added dropwise to the dithiodipyridine solution, the dropwise addition was completed, the mixture was stirred overnight at room temperature, after the reaction was completed, the methanol was dried by spinning, and the mixture was purified by column chromatography to obtain 1.67g of hydroxyethyl dithiopyridine (pale yellow semisolid, 3a) with a yield of 89%.
(3) Preparation of intermediate 4 c: 2.44g (6.14mmol) of intermediate 2c was dissolved in anhydrous dichloromethane, 1.38g (7.27mmol) of intermediate 3a was added and dissolved by stirring, 1.52g (7.37mmol) of DCC (dehydrating agent) and 0.9g (7.37mmol) of DMAP (catalyst) were added and dissolved, and the mixture was stirred overnight at room temperature, after completion of the reaction, diluted hydrochloric acid solution, saturated sodium bicarbonate solution and water were sequentially used, and finally dried over anhydrous sodium sulfate, followed by suction filtration and spin drying, and column chromatography separation to obtain 2.4g of a saturated aliphatic chain (pale yellow solid, 4c) having a dithiopyridine attached to the terminal thereof in a yield of 70%.
(4) Preparation of intermediate 5 c: dissolving 5.67g (10mmol) of the intermediate 4c in 20mL of DMF to obtain a DMF solution of the intermediate 4c, then dissolving 3.65g (10mmol) of reduced glutathione in 10mL of water to obtain a reduced glutathione aqueous solution, adding the reduced glutathione aqueous solution into the DMF solution, stirring overnight until the system turns yellow, placing the system in a dialysis bag, removing the DMF in the system, and precipitating 6.56g of white solid, namely the amphiphilic biological supramolecule (5b), wherein the yield is 85%.
(5) Preparing an organic framework nanofiber tube: and (3) placing 5mg of 5c into 5mL of deionized water, carrying out ultrasonic self-assembly at the ultrasonic frequency of 100Hz and the temperature of 25 ℃ for 10min, then adjusting the ultrasonic frequency to 50Hz, continuing to carry out ultrasonic treatment for 100min, and standing to obtain the organic framework nanofiber tube.
The reaction process is as follows:
effect example 1
The specific surface area, the diameter distribution and the length of the nanofiber tubes of the organic framework fiber tubes prepared in examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. The preparation method of the organic framework nanofiber tube is characterized by comprising the following steps of:
(1) carrying out ring-opening addition reaction on fatty alcohol and succinic anhydride to prepare saturated fatty acid;
(2) carrying out disulfide bond exchange reaction on mercaptoethanol and dipyridyl disulfide to prepare hydroxyethyl dipyridyl disulfide;
(3) mixing saturated fatty acid and hydroxyethyl dithiopyridine, and carrying out esterification reaction under the action of a catalyst to obtain a saturated fatty chain with the tail end connected with the dithiopyridine;
(4) preparing an amphiphilic biological supramolecule by carrying out a disulfide bond exchange reaction on a saturated fatty chain with the tail end connected with dithiopyridine and reduced glutathione;
(5) and self-assembling by using amphiphilic biological supermolecules as a raw material to prepare the organic framework nano fiber tube.
2. The method for preparing organic framework nanofiber tube as claimed in claim 1, wherein the number of carbon atoms of the aliphatic alcohol in the step (1) is more than 0.
3. The method of claim 2, wherein the fatty alcohol comprises myristyl alcohol, undecyl alcohol, arachidyl alcohol, and the like.
4. The method for preparing the organic framework nanofiber tube as claimed in claim 1, wherein the molar ratio of the fatty alcohol to the succinic anhydride in the step (1) is 1: 1-1: 2.
5. The method for preparing the organic framework nanofiber tube as claimed in claim 1, wherein the molar ratio of mercaptoethanol to dithiodipyridine in step (2) is 1: 1.2-1: 3.
6. The method for preparing the organic framework nanofiber tube as claimed in claim 1, wherein the molar ratio of the saturated fatty acid to the hydroxyethyl dipyridyl disulfide in the step (3) is 1: 1-1: 2; the catalyst is 4-dimethylamino pyridine.
7. The method for preparing organic framework nanofiber tube as claimed in claim 1, wherein the molar ratio of the saturated fatty chain of the end-linked dithiopyridine and the reduced glutathione in step (4) is 1:1.
8. The method for preparing organic framework nanofiber tube as claimed in claim 1, wherein the self-assembly of step (5) specifically comprises: self-assembly is carried out under the ultrasonic condition; the ultrasonic power is 50-100 Hz, the temperature is 25-30 ℃, and the time is 30-120 min.
9. An organic framework nanofiber tube prepared by the preparation method of the organic framework nanofiber tube as claimed in any one of claims 1 to 8.
10. The use of the organic framework nanofiber tube as claimed in claim 9 in the fields of catalysis, separation and sensing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210161339.4A CN114471706B (en) | 2022-02-22 | 2022-02-22 | Preparation method of organic framework nanofiber tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210161339.4A CN114471706B (en) | 2022-02-22 | 2022-02-22 | Preparation method of organic framework nanofiber tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114471706A true CN114471706A (en) | 2022-05-13 |
| CN114471706B CN114471706B (en) | 2022-12-09 |
Family
ID=81482021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210161339.4A Active CN114471706B (en) | 2022-02-22 | 2022-02-22 | Preparation method of organic framework nanofiber tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114471706B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136956A (en) * | 1998-03-13 | 2000-10-24 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Fibrous assembly of peptide lipid and method for the preparation thereof |
| US20090202641A1 (en) * | 2006-06-14 | 2009-08-13 | National Institute Of Advanced Industrial Science And Technology | Hollow fibrous organic nanotube and production method thereof |
| CN101792150A (en) * | 2010-03-26 | 2010-08-04 | 昆明理工大学 | Method for preparing stimuli-responsive silicon dioxide nano particle |
| CN110327979A (en) * | 2019-07-29 | 2019-10-15 | 东南大学 | A kind of preparation method of porous hydrophilic nano flower carried metal nanocatalyst |
| CN111040180A (en) * | 2020-01-15 | 2020-04-21 | 重庆大学 | Biological cascade reaction type photodynamic integrated biopolymer and preparation method and application thereof |
| CN113105614A (en) * | 2021-04-08 | 2021-07-13 | 湘潭大学 | Easily degradable responsive core-crosslinkable amphiphilic block polymer, preparation method thereof and application of polymer as drug carrier |
| CN113173882A (en) * | 2021-04-25 | 2021-07-27 | 南开大学 | Pyridyl amphiphilic and electronegative compound and application thereof |
| CN113730595A (en) * | 2021-08-26 | 2021-12-03 | 北京工业大学 | Multifunctional nano-carrier with drug resistance and dual responsiveness of hypoxia/glutathione and preparation method and application thereof |
-
2022
- 2022-02-22 CN CN202210161339.4A patent/CN114471706B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136956A (en) * | 1998-03-13 | 2000-10-24 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Fibrous assembly of peptide lipid and method for the preparation thereof |
| US20090202641A1 (en) * | 2006-06-14 | 2009-08-13 | National Institute Of Advanced Industrial Science And Technology | Hollow fibrous organic nanotube and production method thereof |
| CN101792150A (en) * | 2010-03-26 | 2010-08-04 | 昆明理工大学 | Method for preparing stimuli-responsive silicon dioxide nano particle |
| CN110327979A (en) * | 2019-07-29 | 2019-10-15 | 东南大学 | A kind of preparation method of porous hydrophilic nano flower carried metal nanocatalyst |
| CN111040180A (en) * | 2020-01-15 | 2020-04-21 | 重庆大学 | Biological cascade reaction type photodynamic integrated biopolymer and preparation method and application thereof |
| CN113105614A (en) * | 2021-04-08 | 2021-07-13 | 湘潭大学 | Easily degradable responsive core-crosslinkable amphiphilic block polymer, preparation method thereof and application of polymer as drug carrier |
| CN113173882A (en) * | 2021-04-25 | 2021-07-27 | 南开大学 | Pyridyl amphiphilic and electronegative compound and application thereof |
| CN113730595A (en) * | 2021-08-26 | 2021-12-03 | 北京工业大学 | Multifunctional nano-carrier with drug resistance and dual responsiveness of hypoxia/glutathione and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114471706B (en) | 2022-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102872886B (en) | Preparation method and application of tellurium-based precious metal alloy nanowire catalyst | |
| CN107299417A (en) | A kind of WO3/ZnWO4Preparation method of composite micro-nano rice fiber and products thereof | |
| JP3985025B2 (en) | Amphiphilic compound, soluble carbon nanotube composite | |
| CN101733148A (en) | Magnetic heteropolyacid catalyst, preparing method and application thereof | |
| CN111250114A (en) | Superfine bismuth-rich bismuth oxybromide nanotube prepared by hydrothermal method and application thereof | |
| CN114471706B (en) | Preparation method of organic framework nanofiber tube | |
| CN103789876A (en) | Synthetic method of strip porous lanthanum ferrite nano fibers | |
| CN106083993B (en) | Parents' polypeptide amine dendrimer and preparation method thereof | |
| CN103643350A (en) | Co3O4/In2O3 heterostructure nanotube and preparation method and application thereof | |
| CN113929599B (en) | Precise block polymer nano assembly and preparation method thereof | |
| CN113083272A (en) | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube | |
| CN110817843B (en) | Eutectic solvent, application thereof, carbon quantum dot and preparation method thereof | |
| CN112006019A (en) | Preparation method of halloysite-based nano drug-loaded material | |
| CN110681875B (en) | Isosteviol metal gel and preparation method and application thereof | |
| CN107413358B (en) | Black phosphorus quantum dot/attapulgite nano composite material and preparation method and application thereof | |
| CN110591107B (en) | Nano crystal of supermolecule organic framework material based on dimeric tertiary alcohol and preparation method and application thereof | |
| CN112142613B (en) | Rosin-based small-molecule organic gel and cyclohexane gel formed by same | |
| CN113501886B (en) | Cellulose nano-silver composite material and preparation method and application thereof | |
| CN110357873B (en) | Organic fluorescent material for ultrahigh-resolution cell imaging and preparation and application thereof | |
| CN112279984B (en) | Method for preparing catalytic nano microsphere by polymerization-induced self-assembly | |
| CN105884676B (en) | The preparation method of fullerene-polyoxometallate hybrid molecule | |
| CN114735671B (en) | Nitrogen-doped carbon microsphere as well as preparation method and application thereof | |
| Du et al. | The self-assembly of [60] fullerene-substituted 2, 2′-bipyridine on the surface of Au (111) and Au nanoparticles | |
| CN115259235A (en) | Simple synthesis method of three-dimensional ferric oxide with haystack structure formed by stacking nano short rods | |
| CN113214271A (en) | Continuous preparation method of micron granular CL-20/HMX eutectic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |