CN102775526A - Mono-[6-(8'-amino-3',6'-dioxaoctylamino)]-beta-cyclodextrin and preparation method and application thereof in modified carbon nano tube - Google Patents
Mono-[6-(8'-amino-3',6'-dioxaoctylamino)]-beta-cyclodextrin and preparation method and application thereof in modified carbon nano tube Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 42
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 31
- 229960004853 betadex Drugs 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 56
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 13
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 13
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 238000006396 nitration reaction Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 230000003292 diminished effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229960004839 potassium iodide Drugs 0.000 claims description 3
- 235000007715 potassium iodide Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- -1 cyclodextrin modified carbon nano tube Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- 229920001353 Dextrin Polymers 0.000 description 26
- 239000004375 Dextrin Substances 0.000 description 26
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- 238000002411 thermogravimetry Methods 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 108010025880 Cyclomaltodextrin glucanotransferase Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
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- 238000000015 thermotherapy Methods 0.000 description 1
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Images
Abstract
A cyclodextrin modified water-soluble carbon nano tube is obtained through reaction between mono-[6-(8'-amino-3',6'-dioxaoctylamino)]-beta-cyclodextrin and a carboxylated carbon nano tube, cyclodextrin is connected with the carboxylated carbon nano tube through 1,8-diamido-3',6'-dioxaoctane by an amido bond, and the carbon nano tube is modified by beta-cyclodextrin in a covalent mode. The cyclodextrin molecules in the cyclodextrin modified carbon nano tube and the carbon nano tube are in covalent connection through hydrophilic 1,8-diamido-3,6-dioxaoctane, the cyclodextrin molecules and a triethylene glycol connecting arm effectively improve water-solubility of the carbon nano tube, and the modified carbon nano tube is environment-friendly and has good stability. Preparation conditions are easy to achieve, raw materials are easy to achieve, and cost is low. The mono-[6-(8'-amino-3',6'-dioxaoctylamino)]-beta-cyclodextrin effectively improves hydrophily and biocompatibility of the carbon nano tube. The invention further discloses a preparation method of the mono-[6-(8'-amino-3',6'-dioxaoctylamino)]-beta-cyclodextrin.
Description
Technical field
The present invention relates to a kind of Schardinger dextrins of modification and the carboxylic carbon nano-tube of modifying with it.
Background technology
Carbon nanotube has particular structure and physicochemical property, like the one dimension Nano structure of hollow tubular high length-diameter ratio, high specific surface area, extremely low density, remarkable physical strength, excellent electroconductibility, good heat and chemicalstability, outstanding biocompatibility etc.In recent years, in the crossing domain of Materials science and life science, like drug delivery system, novel biomaterial and biosensor etc., carbon nanotube receives attention more and more widely.
Carbon nanotube can be counted as the monodimension nanometer material by the curling hollow tubular that forms of graphite flake layer, and is different according to the number of graphite flake layer, can be divided into single wall (SWNT) He Duobi (MWNT) carbon nanotube.In the application facet of biomedicine field, carbon nanotube shows many advantages: the carbon nanotube of modifying through hydrophilization has excellent biological compatibility, long body also can slowly be excreted cycling time; High specific surface area can make carbon nanotube loaded a large amount of functional moleculars such as medicine; Particular structure can make carbon nanotube be easy to break through the cytolemma barrier and get into cell, thereby effectively loaded drugs molecule etc. is delivered in the cell; In addition, carbon nanotube also has unique physical optics performance, but heats up like adsorbing close infrared light or radio frequency electromagnetic, potential using value is arranged aspect the thermotherapy organizing deeply, and possibly realize the Synergistic treatment with chemotherapy; Can launch near-infrared fluorescent and have the resonance Raman scattering characteristic, thereby be easy to the intravital carbon nanotube of spike, make carbon nanotube can be used for living imaging and in-vivo diagnostic.Though the research of carbon nanotube aspect biological medicine is also at the experimental stage, its application prospect is encouraging.
Carbon nanotube itself does not contain any active function groups, and has the hydrophobicity of height, therefore will be implemented in the application of biomedicine field, must at first pass through effective hydrophilic modification, but this remains a difficult point for carbon nanotube.At present, the hydrophilic modification of carbon nanotube is mainly introduced enough molecular weight polyethylene glycol (PEG) through the coating of covalently bound or amphiphilic compound and is realized.
Schardinger dextrins (Cyclodextrin is abbreviated as CD) is the general name of amylose starch a series of cyclic oligosaccharides of generation under the effect of the cyclomaltodextrin glucanotransferase that is produced by genus bacillus, has good biocompatibility and degradation property.Common Schardinger dextrins has three kinds of α, β, γ-Huan Hujing, is made up of 6,7,8 glucopyranose units respectively, and wherein beta-cyclodextrin is because production cost is low, and applied range is that industry is at present gone up and used maximum Schardinger dextrins.Cyclodextrin molecular has slightly tapered cylinder-like structure, and its outer rim is hydrophilic and inner chamber is hydrophobic, and forming inclusion compound with guest molecule is one of most important character of Schardinger dextrins.In addition, its chirality cavity has asymmetric induction, some organic reaction of selectivity catalysis and some molecule of selective binding or ionic characteristic again.Therefore Schardinger dextrins all has broad application prospects at numerous areas such as functional materials, medicine transmission, analytical separation.
With the covalently bound surface of Schardinger dextrins at carbon nanotube; Not only can improve the solvability and the operability of carbon nanotube greatly, and the clathration of cyclodextrin molecular chirality cavity and contained great amount of hydroxy group thereof are that the secondary functionization of carbon nanotube provides strong platform.
Summary of the invention
First purpose of the present invention provides a kind of Schardinger dextrins covalent modification carbon nanotube and its preparation method, wherein comprises the compound method of the amino cyclodextrin derivative of band.
Technical scheme of the present invention is following:
A kind of beta-cyclodextrin of modification; It is that list-[6-(8 '-amino-3 '; 6 '-dioxa is hot amino)]-beta-cyclodextrin, it has following structure:
.
A kind of method for making of beta-cyclodextrin of above-mentioned modification, it is with list-(6-O-p-toluenesulfonyl)-beta-cyclodextrin (2.0 g, 1.55 mmol); Potassiumiodide (0.025 g, 0.15 mmol) and 1,8-diamino--3; 6-dioxa octane (0.741 g, 5 mmol) is dissolved in 5 ml exsiccant
N-SL 1332 stirred 4-8 hour down at 70 ℃, behind the cool to room temperature with 100 ml alcohol dilutions; The deposition that filtration under diminished pressure collect to produce and wash to remove with 100 ml ethanol and 50 ml ether successively excessive 1,8-diamino--3,6-dioxa octane; Vacuum-drying gets crude product; Crude product is water-soluble, and get pure article with the Zeo-karb purifying, be designated as CD-NH
2
The application of the beta-cyclodextrin of above-mentioned modification in carbon nano-tube modified.
A kind of carbon nanotube of Schardinger dextrins covalent modification, it is (to be designated as CD-NH by single-[6-(8 '-amino-3 ', 6 '-dioxa is hot amino)]-beta-cyclodextrin
2) obtain with the reaction of carboxylated carbon nanotube, Schardinger dextrins is with 1,8-diamino--3,6-dioxa octane carbon nanotube that be connected with carboxylated carbon nanotube with amido linkage, the beta-cyclodextrin covalent modification.
A kind of method for preparing the carbon nanotube of above-mentioned Schardinger dextrins covalent modification, it comprises the steps:
Step 1. is scattered in 2 g multi-walled carbon nano-tubes (MWNTs) in the nitration mixture of the 100 ml vitriol oils and concentrated nitric acid, and supersound process 12 ~ 36 hours gets carboxylated carbon nanotube after centrifugal, filtration, washing and drying, be designated as MWNT-COOH;
The method of the carbon nanotube of above-mentioned preparation Schardinger dextrins covalent modification; The vitriol oil of the nitration mixture described in the step 1 and the concentration of concentrated nitric acid are respectively 98% and 65%; The volume ratio of the vitriol oil and concentrated nitric acid is 3/1 in the nitration mixture; The power that is used for the ultrasonic apparatus of supersound process is 100 W, and the time of supersound process is 12 ~ 36 hours.
The list that contains amino that the present invention relates to-[6-(8 '-amino-3 ', 6 '-dioxa is hot amino)]-beta-cyclodextrin (CD-NH
2), its chemical structure clear and definite (shown in the ESI-MS figure of Fig. 2) helps further functionalization and application with the carbon nanotube after its modification; In addition; Pass through 1 between cyclodextrin molecular and the carbon nanotube, 8-diamino--3,6-dioxa octane connects; Can effectively improve the wetting ability of modifying the back carbon nanotube, more help its application at aspects such as biological medicines.
Description of drawings:
Fig. 1 is the reaction scheme of Schardinger dextrins covalent modification carbon nanotube;
Fig. 2 contains amino cyclodextrin derivative (CD-NH
2) the ESI-MS spectrogram;
Fig. 3 be carboxylic carbon nano-tube (MWNT-COOH) (3a), single-[6-(8 '-amino-3 ', 6 '-dioxa is hot amino)]-beta-cyclodextrin (CD-NH
2) (3b) with multi-walled carbon nano-tubes (MWNT-CD) infrared spectrogram (3c) of Schardinger dextrins covalent modification;
Fig. 4 be carboxylic carbon nano-tube (MWNT-COOH) (4a) with multi-walled carbon nano-tubes (MWNT-CD) thermogravimetric analysis (TGA) (4b) of Schardinger dextrins covalent modification.
Embodiment:
Embodiment 1, the preparation of carboxylated carbon nanotube:
2 g multi-walled carbon nano-tubes (MWNTs) are scattered in the nitration mixture of the 100 ml vitriol oils and concentrated nitric acid; Supersound process 12 hours; After operations such as centrifugal, filtration, washing and drying carboxylated carbon nanotube is designated as MWNT-COOH (ir spectra such as Fig. 3 a, TGA such as Fig. 4 is a).The wherein used vitriol oil and the concentration of concentrated nitric acid are respectively 98% and 65%, and the volume ratio of the vitriol oil and concentrated nitric acid is 3/1 in the nitration mixture, and the power that is used for the ultrasonic apparatus of supersound process is 100 W.
The preparation of the carbon nanotube that embodiment 2. is carboxylated:
The present embodiment step is with embodiment 1, but the supersound process time change 24 hours into, the ir spectra of the carboxylated carbon nanotube of gained and TGA figure are basic identical with embodiment's 1.
The preparation of the carbon nanotube that embodiment 3. is carboxylated:
The present embodiment step is with embodiment 1, but the supersound process time change 36 hours into, the ir spectra of the carboxylated carbon nanotube of gained and TGA figure are basic identical with embodiment's 1.
Embodiment 4. single-[6-(8 '-amino-3 ', 6 '-dioxa is hot amino)]-beta-cyclodextrin (CD-NH
2) preparation:
With list-(6-O-p-toluenesulfonyl)-beta-cyclodextrin (2.0 g, 1.55 mmol), potassiumiodide (0.025 g, 0.15 mmol) and 1,8-diamino--3,6-dioxa octane (0.741 g, 5 mmol) is dissolved in 5 ml exsiccant
N-SL 1332 stirred 4-8 hour down at 70 ℃, behind the cool to room temperature with 100 ml alcohol dilutions.The deposition that filtration under diminished pressure collect to produce and wash to remove with 100 ml ethanol and 50 ml ether successively excessive 1,8-diamino--3,6-dioxa octane, vacuum-drying gets crude product.Crude product is water-soluble, and get pure article with the Zeo-karb purifying, be designated as CD-NH
2, its ir spectra is seen Fig. 3 b, ESI-MS (
M/z): Calcd. 1264.48, found:633.17 for [M+2H]
2+, 1265.33 for [M+H]
+(see figure 2)..
The preparation of the multi-walled carbon nano-tubes of embodiment 5. Schardinger dextrins covalent modifications:
With 100 mg MWNT-COOH, 21 mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC*HCl), 13 mg
N-HOSu NHS (NHS), 24 μ l triethylamines and 139 mg CD-NH
2Ultra-sonic dispersion is in 5 ml DMF, and the gained mixture is stirred overnight at room temperature.Add 5 ml acetone; Centrifugal collection solid, and being scattered in the water is fully dialysis in 10,000 the dialysis tubing at molecular weight cut-off; Obtain the multi-walled carbon nano-tubes of the Schardinger dextrins covalent modification of purifying after the vacuum-drying; Wherein the content of Schardinger dextrins is about 0.20 mmol/g, and its ir spectra is seen Fig. 3 c, and TGA sees Fig. 4 b.
The preparation of the multi-walled carbon nano-tubes of embodiment 6. Schardinger dextrins covalent modifications:
Present embodiment is identical with the method for embodiment 5, but adopts the MWNT-COOH of embodiment 2 preparations.The ir spectra of the multi-walled carbon nano-tubes of gained Schardinger dextrins covalent modification and TGA and embodiment's 5 is basic identical, and the content of Schardinger dextrins is about 0.26 mmol/g in the multi-walled carbon nano-tubes of gained Schardinger dextrins covalent modification.
The preparation of the multi-walled carbon nano-tubes of embodiment 7. Schardinger dextrins covalent modifications:
Present embodiment is identical with the method for embodiment 5, but adopts the MWNT-COOH of embodiment 3 preparations.The ir spectra of the multi-walled carbon nano-tubes of gained Schardinger dextrins covalent modification and TGA and embodiment's 5 is basic identical, and the content of Schardinger dextrins is about 0.31 mmol/g in the multi-walled carbon nano-tubes of gained Schardinger dextrins covalent modification.
Claims (6)
1. the beta-cyclodextrin of a modification; It is characterized in that: it is that list-[6-(8 '-amino-3 '; 6 '-dioxa is hot amino)]-beta-cyclodextrin, it has following structure:
.
2. the method for making of the beta-cyclodextrin of the described modification of claim 1; It is characterized in that: it is with list-(6-O-p-toluenesulfonyl)-beta-cyclodextrin (2.0 g, 1.55 mmol), potassiumiodide (0.025 g; 0.15 mmol) with 1; 8-diamino--3,6-dioxa octane (0.741 g, 5 mmol) is dissolved in 5 ml exsiccant
N-SL 1332 stirred 4-8 hour down at 70 ℃, behind the cool to room temperature with 100 ml alcohol dilutions; The deposition that filtration under diminished pressure collect to produce is also washed to remove excessive 1 with 100 ml ethanol and 50 ml ether successively; 8-diamino--3,6-dioxa octane, vacuum-drying gets crude product; Crude product is water-soluble, and get pure article with the Zeo-karb purifying.
3. the application of the beta-cyclodextrin of the described modification of claim 1 in carbon nano-tube modified.
4. the carbon nanotube of the beta-cyclodextrin covalent modification of the described modification of claim 1; It is characterized in that: it is by single-[6-(8 '-amino-3 '; 6 '-dioxa is hot amino)]-beta-cyclodextrin obtain with carboxylated carbon nanotube reaction, single-[6-(8 '-amino-3 ', the hot amino of 6 '-dioxa)]-beta-cyclodextrin carbon nanotube that be connected with carboxylated carbon nanotube with amido linkage, the beta-cyclodextrin covalent modification.
5. the method for the carbon nanotube of a beta-cyclodextrin covalent modification for preparing the described modification of claim 4 is characterized in that it comprises the steps:
Step 1. is scattered in 2 g multi-walled carbon nano-tubes (MWNTs) in the nitration mixture of the 100 ml vitriol oils and concentrated nitric acid, and supersound process 12 ~ 36 hours gets carboxylated carbon nanotube after centrifugal, filtration, washing and drying, be designated as MWNT-COOH;
Step 2. is with 100 mg MWNT-COOH, 21 mg 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl), 13 mg
N-HOSu NHS (NHS), 24 μ l triethylamines and 139 mg list-[6-(8 '-amino-3 ', 6 '-dioxa is hot amino)]-beta-cyclodextrin ultra-sonic dispersion is in 5 ml
N,
NIn-the N, the gained mixture is stirred overnight at room temperature, adds 5 ml acetone, and centrifugal collection solid, and being scattered in the water is fully dialysis in 10,000 the dialysis tubing at molecular weight cut-off, cyclodextrin modified multi-walled carbon nano-tubes.
6. the method for the carbon nanotube of the beta-cyclodextrin covalent modification of preparation modification according to claim 5; It is characterized in that: the vitriol oil of the nitration mixture described in the step 1 and the concentration of concentrated nitric acid are respectively 98% and 65%; The volume ratio of the vitriol oil and concentrated nitric acid is 3/1 in the nitration mixture; The power that is used for the ultrasonic apparatus of supersound process is 100 W, and the time of supersound process is 12 ~ 36 hours.
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| CN107668036A (en) * | 2017-10-31 | 2018-02-09 | 西南大学 | Tobacco bacterial wilt controlling agent containing dephnetin and preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU187360B (en) * | 1981-09-22 | 1985-12-28 | Chinoin Gyogyszer Es Vegyeszet | Komplex-forming cyclodextrine-crown-ether derivatives and process for producing them |
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
| CN1617890A (en) * | 2001-11-30 | 2005-05-18 | 真塔萨卢斯有限责任公司 | Cyclodextrin grafted biocompatible amphiphilic polymer and methods of preparation and use thereof |
| CN102140145A (en) * | 2011-01-24 | 2011-08-03 | 哈尔滨工业大学 | Method for grafting carbon nanotubes by using cyclodextrin |
-
2012
- 2012-07-13 CN CN2012102423891A patent/CN102775526A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU187360B (en) * | 1981-09-22 | 1985-12-28 | Chinoin Gyogyszer Es Vegyeszet | Komplex-forming cyclodextrine-crown-ether derivatives and process for producing them |
| CN1617890A (en) * | 2001-11-30 | 2005-05-18 | 真塔萨卢斯有限责任公司 | Cyclodextrin grafted biocompatible amphiphilic polymer and methods of preparation and use thereof |
| CN1436721A (en) * | 2002-02-08 | 2003-08-20 | 中国科学院化学研究所 | Prepn of water soluble carbon nanotube |
| CN102140145A (en) * | 2011-01-24 | 2011-08-03 | 哈尔滨工业大学 | Method for grafting carbon nanotubes by using cyclodextrin |
Non-Patent Citations (2)
| Title |
|---|
| LILI LI ET AL.: "《Protein Adsorption on Functionalized Multiwalled Carbon Nanotubes with Amino-Cyclodextrin》", 《AICHE JOURNAL》, vol. 57, no. 12, 28 February 2011 (2011-02-28) * |
| 童林荟著: "《环糊精化学-基础与应用》", 31 March 2001, 科学出版社, article "《环糊精化学-基础与应用》" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107668036A (en) * | 2017-10-31 | 2018-02-09 | 西南大学 | Tobacco bacterial wilt controlling agent containing dephnetin and preparation method and application |
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