CN104031173A - Chitosan bipyridyl quaternary ammonium salts, and preparation method and application thererof - Google Patents
Chitosan bipyridyl quaternary ammonium salts, and preparation method and application thererof Download PDFInfo
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Abstract
The invention relates to daily chemical field and pharmaceutical industry, and concretely relates to chitosan bipyridyl quaternary ammonium salts, and a preparation method and application thererof. The chitosan bipyridyl quaternary ammonium salt derivatives qcts2Py, qcts3Py or qcts4Py shown as a formula (1), (2) or (3). The preparation method comprises: taking chitosan as a raw material, reacting with excessive corresponding pyridine aldehyde, so as to synthesize a corresponding Schiff alkali, then reducing by using sodium borohydride to obtain N-substituted chitosan, and then reacting with iodomethane, so as to obtain the chitosan bipyridyl quaternary ammonium salt derivative. Compared with the chitosan raw material, the chitosan bipyridyl quaternary ammonium salt derivatives have good anti-oxidation activity. The chitosan bipyridyl quaternary ammonium salt derivatives are synthesized through the effective synthetic means, also the chitosan bipyridyl quaternary ammonium salt derivatives are relatively good in water solubility and substantially improved in anti-oxidation activity, helps to enhance the bioactivity of chitosan and expand the application scope of chitosan, and are applicable to fields of daily chemicals, pharmaceutical industries and the like.
Description
Technical field
The present invention relates to household chemicals field and pharmaceutical industries, is specifically a kind of preparation method and application of Chitosan double quaternary ammonium salt derivative.
Background technology
Chitosan (Chitosan) is that a kind of source is abundant, occurring in nature be only second to cellulose output renewable, have no side effect, the natural glycosaminoglycan that biocompatibility and degradation property are good, himself and derivative thereof have physiology, the pharmacological function character of many uniquenesses, are widely used in the multiple industry fields such as medicine, food, agricultural, daily use chemicals, environmental protection.The structure that chitosan itself is special and character, have sterilization, bacteriostatic activity, and nontoxic, free of contamination characteristic, can be used as the object of modification to developing secondary lead compound.Reactive group in chitosan molecule has hydroxyl and amino, can be used as the effect group while modification.But water-soluble poor due to chitosan itself, has had a strong impact on the use range of chitosan, by the chemically modified to chitosan, can obtain water-soluble good derivative, expands the use range of chitosan.
Pyridine and its derivatives is indispensable important source material and the intermediates in field such as current chemical field Chinese materia medica, agricultural chemicals, tensio-active agent, synthetic materials, and purposes is very extensive.Closely during the last ten years, the application in agricultural chemicals and medical research field to pyridine and its derivatives both at home and abroad, particularly gives and great attention the development research of nitrogen heterocyclic, fluorine-containing compound.
Summary of the invention
The object of this invention is to provide a kind of preparation method and application of Chitosan double quaternary ammonium salt derivative.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of chitosan Bispyridinium salts, Chitosan double quaternary ammonium salt derivative is qcts2Py, qcts3Py or the qcts4Py shown in formula (1), (2) or (3);
Wherein the average span of n is 62-1242.
A kind of preparation method of chitosan Bispyridinium salts, it is in 2% acetum that raw materials of chitosan is dissolved in volume ratio, and after dissolving, chitosan is added to respectively in 2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde of dehydrated alcohol, continues respectively to stir 1-2h, stir evenly rear 10% sodium borohydride that drips respectively, then stir 1-2h, after stirring, impouring, to excessive acetone, precipitates respectively again, suction filtration, 60 DEG C of oven dry, grind, and obtain respectively the pressed powder of the chitosan derivatives of N replacement;
The pressed powder of getting the chitosan derivatives of above-mentioned gained N replacement is scattered in respectively in METHYLPYRROLIDONE, stirring at room temperature 8-12h, after stirring, add again respectively sodium hydroxide, methyl iodide and sodium iodide, after adding, stir 8-16h respectively at 25-60 DEG C, react complete impouring respectively to excessive acetone, precipitation, suction filtration, washing with acetone, oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
After described dissolving chitosan respectively with 2-pyridylaldehyde, 3-pyridylaldehyde or 4-pyridylaldehyde dehydrated alcohol exist in stirring reaction 1-2h, obtain respectively N replace chitosan derivatives; Wherein the add-on of 2-pyridylaldehyde, 3-pyridylaldehyde or 4-pyridylaldehyde is 3 times of chitosan monomer molar amount after dissolving.
The pyridine chitosan that described N replaces is scattered in respectively in METHYLPYRROLIDONE, stirring at room temperature 8-12h, and after stirring, difference drips 1mol/L sodium hydroxide, methyl iodide and the sodium iodide of 200mL again with per minute 2mL speed; The 1-2 that wherein add-on of methyl iodide and sodium iodide is respectively raw materials of chitosan monomer molar number doubly.
The pyridine chitosan that N replaces is scattered in respectively in METHYLPYRROLIDONE, and stirring at room temperature 8-12h, adds respectively sodium hydroxide, methyl iodide and sodium iodide again after stirring, then at 25-60 DEG C, react 8-16h.
The present invention has advantages of: the principle that the present invention superposes by activity, and the method for employing chemically modified, design synthetic route, prepares novel chitosan derivatives, to improving the biological activity of chitosan, expands use range.Specifically obtain novel Chitosan double quaternary ammonium salt derivative by effective synthesizing mean, synthesis step is simple, and cost is lower, is introducing after active stronger pyridine quaternary ammonium salt group, has weakened on the one hand the hydrogen bond action of chitosan, has improved that it is water-soluble; On the other hand, this pyridine quaternary ammonium salt group itself has good anti-oxidant activity, can further improve chitosan at agricultural chemicals, the use of the aspects such as medicine.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of chitosan.
Fig. 2 is the infrared spectrogram of the chitosan 2-pyridine bi-quaternary ammonium salt derivative of embodiment of the present invention acquisition.
Fig. 3 is the infrared spectrogram of the chitosan 3-pyridine bi-quaternary ammonium salt derivative of embodiment of the present invention acquisition.
Fig. 4 is the infrared spectrogram of the chitosan 4-pyridine bi-quaternary ammonium salt derivative of embodiment of the present invention acquisition.
Embodiment
Embodiment 1
Chitosan double quaternary ammonium salt is the compound shown in formula 1, formula 2 and formula 3.
The preparation of Chitosan double quaternary ammonium salt: it is in 2% acetum that 1.61g chitosan is dissolved in 50mL volume ratio, after dissolving, chitosan is added to respectively the 30mmol2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde that are dissolved in 10mL dehydrated alcohol, under room temperature, continue to stir 2h, after stirring, drip 45mmol sodium borohydride with per minute 2mL speed, stir 2h, stir in the excessive acetone of rear impouring, precipitation, suction filtration, 60 DEG C of oven dry, grind, obtain respectively the pressed powder of the chitosan derivatives of N replacement.Getting the upper step of 0.5g gained pressed powder is scattered in respectively in 30mL METHYLPYRROLIDONE, stirring at room temperature 12h, add 0.1mL1M sodium hydroxide solution, 0.75g sodium iodide and 4mL methyl iodide, 50 DEG C are stirred 20h, react in the excessive acetone of complete impouring, precipitation, suction filtration, washing with acetone 3 times, 60 DEG C of oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
From Fig. 2, Fig. 3 with Fig. 4 compared with Fig. 1 chitosan raw material, 1631.48cm
-1, 1631.89cm
-1, 1643.05cm
-1for quaternary ammonium salt absorption peak.779.10cm
-1, 806.10cm
-1, 813.81cm
-1charateristic avsorption band (Feng Changgen, Bai Linshan, Ren Qisheng that the absorption peak at place is pyridine ring; Amino-complex is modified the synthetic and infrared spectroscopic study of Crosslinked Chitosan Resin; Spectroscopy and spectroscopic analysis, 2004,24:1315-1318. Bai Linshan, Lei Hong, square golden seal, Zhang Wanxing, Huang Jun; The sulphur content of barium sulfate Nephelometric Determination thiolated chitosan resin; Su Li, Wang Xiaochuan, Song Hongtao, Guan Huai, remaining Kun; Data and structural analysis are learned in the POP of 2-chloro-5-trichloromethylpyridine; Safety and environment journal, 2005,5:59-61.) prove that bi-quaternary ammonium salt pyridine chitosan synthesizes successfully.
Embodiment 2
Difference from Example 1 is:
The preparation of Chitosan double quaternary ammonium salt derivative: it is in 2% acetum that 1.61g chitosan is dissolved in 50mL volume ratio, after dissolving, be added to respectively in 20mmol2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde that is dissolved in dehydrated alcohol, under room temperature, continue to stir 1.5h, after stirring, drip 45mmol sodium borohydride with per minute 2mL speed, stir 2h, stir in the excessive acetone of rear impouring precipitation, suction filtration, 60 DEG C of oven dry, grind, and obtain respectively the pressed powder of the chitosan derivatives of N replacement.Getting the upper step of 0.5g gained pressed powder is scattered in respectively in 30mL METHYLPYRROLIDONE, stirring at room temperature 12h, add 0.1mL1M sodium hydroxide solution, 0.75g sodium iodide, 4mL methyl iodide, 50 DEG C are stirred 20h, react in the excessive acetone of complete impouring, precipitation, suction filtration, washing with acetone 3 times, 60 DEG C of oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
Embodiment 3
It is in 2% acetum that 1.61g chitosan is dissolved in 50mL volume ratio, after dissolving, chitosan is added to respectively the 30mmol2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde that are dissolved in dehydrated alcohol, under room temperature, continue to stir 2h, after stirring, drip 45mmol sodium borohydride with per minute 2mL speed, stir 2h, stir in the excessive acetone of rear impouring, precipitation, suction filtration, 60 DEG C of oven dry, grind, obtain respectively the pressed powder of the chitosan derivatives of N replacement.Getting the upper step of 0.5g gained pressed powder is scattered in respectively in 30mL METHYLPYRROLIDONE, stirring at room temperature 6h, add 0.1mL1M sodium hydroxide solution, 0.75g sodium iodide, 4mL methyl iodide, 50 DEG C are stirred 20h, react in the excessive acetone of complete impouring, precipitation, suction filtration, washing with acetone 3 times, 60 DEG C of oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
Embodiment 4
It is in 2% acetum that 1.61g chitosan is dissolved in 50mL volume ratio, after dissolving, chitosan is added to respectively the 30mmol2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde that are dissolved in 10mL dehydrated alcohol, under room temperature, continue to stir 2h, after stirring, drip 45mmol sodium borohydride with per minute 2ml speed, stir 2h, stir in the excessive acetone of rear impouring, precipitation, suction filtration, 60 DEG C of oven dry, grind, obtain respectively the pressed powder of the chitosan derivatives of N replacement.Getting the upper step of 0.5g gained pressed powder is scattered in respectively in 30mL METHYLPYRROLIDONE, stirring at room temperature 12h, add 0.1mL1M sodium hydroxide solution, 0.75g sodium iodide, 4mL methyl iodide, 50 DEG C are stirred 20h, react in the excessive acetone of complete impouring, precipitation, suction filtration, washing with acetone 3 times, 60 DEG C of oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
Application examples
Remove the mensuration of hydroxy radical qiao resistance of oxidation:
Measuring respectively above-mentioned synthetic bi-quaternary ammonium salt chitosan removes the ability of hydroxy radical qiao and contrasts: Chitosan double quaternary ammonium salt prepared by embodiment 1-3 and the lyophilize of chitosan material vacuum are to constant weight, prepare respectively desired concn in table one, cumulative volume is that the reaction solution of 4.5mL contains following reagent: the amino lactose of 6-or the lactose solution 1mL of the different concns of preparation, phosphoric acid buffer 1mL (preparation phosphoric acid buffer: get respectively 41.58gNa2HPO4.12H2O, 5.2887gNaH2PO4.2H2O, add water and be dissolved to 1000mL), the kumkum 1mL of 360 μ g/mL, 2mmol/LEDTA-Fe0.5mL and 3% hydrogen peroxide 1mL, reaction solution mixes in test tube, in 37 DEG C of water-baths, react after 30min, working sample is in the absorbancy at 520nm place, blank group 1mL distilled water substitutes test sample, control group 1.0mL distilled water and 1mL phosphoric acid buffer substitute sample and hydrogen peroxide (note: sample is all surveyed twice, average).
Remove hydroxyl radicals (%)=[(the blank 520nm of A sample 520nm-A)/(the blank 520nm of A contrast 520nm-A)] × 100%
Experimental result: it is as shown in table 1 that the Chitosan double quaternary ammonium salt of synthesized and chitosan raw material are removed hydroxyl radicals, and the removing hydroxyl radicals of synthesized Chitosan double quaternary ammonium salt is obviously better than chitosan.
Table 1, the ability (%) of the removing hydroxy radical qiao of amino lactose sugar and lactose
Claims (5)
1. a chitosan Bispyridinium salts, is characterized in that: Chitosan double quaternary ammonium salt derivative is qcts2Py, qcts3Py or the qcts4Py shown in formula (1), (2) or (3);
Wherein the average span of n is 62-1242.
2. one kind according to the preparation method of chitosan Bispyridinium salts claimed in claim 1, it is characterized in that: it is in 2% acetum that raw materials of chitosan is dissolved in volume ratio, after dissolving, chitosan is added to respectively in 2-pyridylaldehyde, 3-pyridylaldehyde or the 4-pyridylaldehyde of dehydrated alcohol, continue respectively to stir 1-2h, stir evenly rear 10% sodium borohydride that drips respectively, then stir again 1-2h, after stirring, difference impouring is to excessive acetone, precipitation, suction filtration, 60 DEG C of oven dry, grind, and obtain respectively the pressed powder of the chitosan derivatives of N replacement;
The pressed powder of getting the chitosan derivatives of above-mentioned gained N replacement is scattered in respectively in METHYLPYRROLIDONE, stirring at room temperature 8-12h, after stirring, add again respectively sodium hydroxide, methyl iodide and sodium iodide, after adding, stir 8-16h respectively at 25-60 DEG C, react complete impouring respectively to excessive acetone, precipitation, suction filtration, washing with acetone, oven dry, obtain the Chitosan double quaternary ammonium salt derivative shown in corresponding formula (1), (2) or (3).
3. by the preparation method of chitosan Bispyridinium salts claimed in claim 2, it is characterized in that: after described dissolving chitosan respectively with 2-pyridylaldehyde, 3-pyridylaldehyde or 4-pyridylaldehyde dehydrated alcohol exist in stirring reaction 1-2h, obtain respectively N replace chitosan derivatives; Wherein the add-on of 2-pyridylaldehyde, 3-pyridylaldehyde or 4-pyridylaldehyde is 3 times of chitosan monomer molar amount after dissolving.
4. by the preparation method of the chitosan Bispyridinium salts described in claim 1 or 2, it is characterized in that: the pyridine chitosan that described N replaces is scattered in respectively in METHYLPYRROLIDONE, stirring at room temperature 8-12h, after stirring, difference drips 1mol/L sodium hydroxide, methyl iodide and the sodium iodide of 200mL again with per minute 2mL speed; The 1-2 that wherein add-on of methyl iodide and sodium iodide is respectively raw materials of chitosan monomer molar number doubly.
5. by the preparation method of chitosan Bispyridinium salts claimed in claim 2, it is characterized in that: the pyridine chitosan that N replaces is scattered in respectively in METHYLPYRROLIDONE, stirring at room temperature 8-12h, after stirring, add again respectively sodium hydroxide, methyl iodide and sodium iodide, then at 25-60 DEG C, react 8-16h.
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CN107383239A (en) * | 2017-08-28 | 2017-11-24 | 中国科学院烟台海岸带研究所 | A kind of N pyridines urea groups chitosan quaternary ammonium salt and its preparation method and application |
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