CN117285662A - 一种壳聚糖双吡啶季铵盐及其制备方法 - Google Patents
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 64
- -1 bipyridine quaternary ammonium salt Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract 8
- 125000001246 bromo group Chemical group Br* 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 7
- FFHRKYGEMWVANQ-UHFFFAOYSA-N 4-[[4-(pyridin-4-ylmethyl)phenyl]methyl]pyridine Chemical compound C=1C=C(CC=2C=CN=CC=2)C=CC=1CC1=CC=NC=C1 FFHRKYGEMWVANQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 14
- 230000001954 sterilising effect Effects 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 2
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- 238000002474 experimental method Methods 0.000 description 10
- 241000222122 Candida albicans Species 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 8
- 241000191967 Staphylococcus aureus Species 0.000 description 8
- 229940095731 candida albicans Drugs 0.000 description 8
- 230000002147 killing effect Effects 0.000 description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 231100000027 toxicology Toxicity 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 238000010181 skin prick test Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- A61P31/04—Antibacterial agents
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
- A61K31/716—Glucans
- A61K31/722—Chitin, chitosan
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
本发明提供了一种壳聚糖双吡啶季铵盐的制备方法,属于医药技术领域。该方法首先将壳聚糖(CS)与溴乙酰溴在低温下反应,制得CS‑Br。随后将CS‑Br与含两个吡啶基团的长链化合物反应,得到水溶性壳聚糖双吡啶季铵盐。得到的壳聚糖双吡啶季铵盐水溶性好,杀菌效率高,毒性与刺激性低,具广光谱杀菌效果。其对皮肤无刺激。
Description
技术领域
本发明属于医药技术领域,具体涉及一种壳聚糖双吡啶季铵盐及其制备方法。
背景技术
随着人们生活水平的提高,对生活中常用杀菌剂的安全性要求越来越高。壳聚糖来源广泛,为天然多糖甲壳素脱除部分乙酰基的产物,具有生物降解性、生物相容性、无毒性、抑菌、抗癌、降脂、增强免疫等多种生理功能,广泛应用于食品添加剂、纺织、农业、环保、美容保健、化妆品、抗菌剂等众多领域。作为新一代的抗菌材料,具有既不溶于水,也不溶于有机溶剂,抗菌效果较差。双季铵盐杀菌效率高,毒性与刺激性低,具广谱杀菌效果。
将壳聚糖改性成壳聚糖双吡啶季铵盐,改善了壳聚糖的水溶性,同时大大提高了其抗菌性。新型壳聚糖双吡啶季铵盐抗菌能力更强,且具有更好的生物相容性,能够应用于手术缝合线、医用敷料等。
发明内容
本发明是针对上述存在的技术问题提供一种壳聚糖双吡啶季铵盐及其制备方法。
本发明的目的可以通过以下技术方案实现:
一种壳聚糖双吡啶季铵盐的制备方法,该方法包括以下步骤:
1)将壳聚糖分散在有机溶剂a中,在温度为3~10 ℃的条件下加入溴乙酰溴进行反应20~24h,反应结束后离心、洗涤和烘干,即可得到含溴端基的壳聚糖 CS-Br;
2)将含两个吡啶基团的长链化合物溶解有机溶剂b中,加入CS-Br,升温回流20~30h,反应结束后将反应溶液离心后上清液加入到透析袋中进行透析,即可得到水溶性壳聚糖双吡啶季铵盐。
本发明技术方案中:步骤1)中所述的溴乙酰溴与壳聚糖的摩尔比为4~8:1~2。
本发明技术方案中:有机溶剂a为甲苯。
本发明技术方案中:壳聚糖在温度为35~40℃的条件下加入到有机溶剂a中并搅拌0.5~1h。
本发明技术方案中:有机溶剂b为醇类溶剂,优选所述的有机溶剂b为乙醇。
本发明技术方案中:含两个吡啶基团的长链化合物为4,4’-(1,3-丙二基)双吡啶(CAS:17252-51-6), 1,4-双(4-吡啶甲基)苯 (CAS:52469-20-2),1,2-双(4-(吡啶-4-基)苯基)乙炔 (1,2-Bis(4-Pyridin-4-Yl)Phenyl)Ethyne) (CAS:1189377-77-2)的至少一种。
本发明技术方案中:含两个吡啶基团的长链化合物与CS-Br的摩尔比0.3~1:1~3。
本发明的有益效果:
本发明设计和制备的壳聚糖双吡啶季铵盐具有以下有益效果:
1,具有杀灭大肠杆菌、金黄色葡萄球菌和白色念珠菌能力,且杀菌率都达到了≧99%;
2,通过毒理实验表明,其对皮肤无刺激,且未见皮肤变态反应。
具体实施方式
以下结合实施例对本发明做进一步说明,但本发明的保护范围不限于此:
实施例1:本发明提供了一种壳聚糖双吡啶季铵盐的制备方法,包括以下步骤:1)将1.61 g壳聚糖 (CS)粉末分散在50 ml甲苯中,升温40℃,搅拌1h,降温至5 ℃,加入溴乙酰溴4.2 g,搅拌24 h,离心,使用去离子水多次洗涤,得到含溴端基的壳聚糖 (CS-Br)。烘干,得到干燥的CS-Br。
2)将0.46 g 4,4’-(1,3-丙二基)双吡啶溶解在50 ml乙醇中,加入2.0 g CS-Br,升温回流24h。得到粗品壳聚糖双吡啶季铵盐。将反应溶液离心后上清液加入到透析袋中,透析一周去除杂质,得到水溶性壳聚糖双吡啶季铵盐。
实施例2:本发明提供了一种壳聚糖双吡啶季铵盐的制备方法,包括以下步骤:1)将1.61 g壳聚糖 (CS) 粉末分散在50 ml甲苯中,升温40 ℃,搅拌1 h,降温至5℃,加入6.0g溴乙酰溴,搅拌24 h,离心,使用去离子水多次洗涤,得到含溴端基的壳聚糖 (CS-Br)。烘干,得到干燥的CS-Br。
2)将0.61 g 1,4-双(4-吡啶甲基)苯溶解在50 ml乙醇中,加入2.0 g CS-Br,升温回流24 h。得到粗品壳聚糖双吡啶季铵盐。将反应溶液离心后上清液加入到透析袋中,透析一周去除杂质,得到水溶性壳聚糖双吡啶季铵盐。
实施例3:本发明提供了一种壳聚糖双吡啶季铵盐的制备方法,包括以下步骤:1)将1.61 g壳聚糖 (CS)粉末分散在50 ml甲苯中,升温40 ℃,搅拌1 h,降温至5 ℃,加入8.0g溴乙酰溴,搅拌24 h,离心,使用去离子水多次洗涤,得到含溴端基的壳聚糖 (CS-Br)。烘干,得到干燥的CS-Br。
2)0.78 g 1,2-双(4-(吡啶-4-基)苯基)乙炔溶解在50 ml乙醇中,加入2.0 g CS-Br,升温回流24 h。得到粗品壳聚糖双吡啶季铵盐。将反应溶液离心后上清液加入到透析袋中,透析一周去除杂质,得到水溶性壳聚糖双吡啶季铵盐。
杀菌实验:
对原料壳聚糖进行杀灭金黄色葡萄球菌、大肠杆菌和白色念珠菌实验,检测在不同作用时间内的杀菌率。结果如下:
表1 壳聚糖杀菌实验结果
对实施例1所得到的壳聚糖双吡啶季铵盐进行杀灭金黄色葡萄球菌、大肠杆菌和白色念珠菌实验,检测在不同作用时间内的杀菌率。结果如下:
表2 实施例1杀菌实验结果
结论:由表1可见,壳聚糖对细菌具有一定的杀伤作用,但杀伤作用不强。由表2可见,实施例1制得的壳聚糖双吡啶季铵盐对金黄色葡萄球菌、大肠杆菌和白色念珠菌均有显著的杀菌作用。
对实施例2所得到的壳聚糖双吡啶季铵盐进行杀灭金黄色葡萄球菌、大肠杆菌和白色念珠菌实验,检测在不同作用时间内的杀菌率。结果如下:
表3 实施例2杀菌实验结果
结论:由表3可见,实施例2制得的壳聚糖双吡啶季铵盐对金黄色葡萄球菌、大肠杆菌和白色念珠菌均有显著的杀菌作用。
对实施例3所得到的壳聚糖双吡啶季铵盐进行杀灭金黄色葡萄球菌、大肠杆菌和白色念珠菌实验,检测在不同作用时间内的杀菌率。结果如下:
表4 实施例3杀菌实验结果
结论:由表4可见,实施例3制得的壳聚糖双吡啶季铵盐对金黄色葡萄球菌、大肠杆菌和白色念珠菌均有显著的杀菌作用。
毒理实验:
对实施例1-3所得到的壳聚糖双吡啶季铵盐进行两项毒理实验。本实验参照《消毒技术规范》2002版第二部分皮肤刺激性试验和皮肤变态反应实验。结果如下表所示:
表5 皮肤刺激性实验结果
结论:由表5可知,本发明制得的壳聚糖双吡啶季铵盐的刺激强度均为轻度刺激性。
表6 皮肤变态反应实验
结论:由表6可知,本发明制得的壳聚糖双吡啶季铵盐对皮肤的致敏率为0。无致敏性。
Claims (7)
1.一种壳聚糖双吡啶季铵盐的制备方法,其特征在于:该方法包括以下步骤:
1)将壳聚糖分散在有机溶剂a中并在温度为35~45℃的条件下搅拌0.5~1.5h,之后在温度为3~10 ℃的条件下加入溴乙酰溴进行反应20~24h,反应结束后离心、洗涤和烘干,即可得到含溴端基的壳聚糖 CS-Br;
2)将含两个吡啶基团的长链化合物溶解有机溶剂b中,加入CS-Br,升温回流20~30 h,反应结束后将反应溶液离心后上清液加入到透析袋中进行透析,即可得到水溶性壳聚糖双吡啶季铵盐。
2.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:步骤1)中所述的溴乙酰溴与壳聚糖的摩尔比为4~8:1~2。
3.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:有机溶剂a为甲苯。
4.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:壳聚糖在温度为35~40℃的条件下加入到有机溶剂a中并搅拌0.5~1h。
5.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:有机溶剂b为醇类溶剂,优选所述的有机溶剂b为乙醇。
6.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:含两个吡啶基团的长链化合物为4,4’-(1,3-丙二基)双吡啶 ,1,4-双(4-吡啶甲基)苯 (CAS:52469-20-2),1,2-双(4-(吡啶-4-基)苯基)乙炔的至少一种。
7.根据权利要求1所述的壳聚糖双吡啶季铵盐的制备方法,其特征在于:含两个吡啶基团的长链化合物与CS-Br的摩尔比0.3~1:1~3。
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