高等学校化学学报 ›› 2024, Vol. 45 ›› Issue (3): 20230375.doi: 10.7503/cjcu20230375
周晓龙1, 汪瑞琪1, 陈国丽1, 郭文明1, 陈飞1, 周炎2, 孙立德2, 汤大保2, 许云辉1()
收稿日期:
2023-08-23
出版日期:
2024-03-10
发布日期:
2024-01-23
通讯作者:
许云辉
E-mail:xuyunhui@ahau.edu.cn
基金资助:
ZHOU Xiaolong1, WANG Ruiqi1, CHEN Guoli1, GUO Wenming1, CHEN Fei1, ZHOU Yan2, SUN Lide2, TANG Dabao2, XU Yunhui1()
Received:
2023-08-23
Online:
2024-03-10
Published:
2024-01-23
Contact:
XU Yunhui
E-mail:xuyunhui@ahau.edu.cn
Supported by:
摘要:
通过香草醛与壳聚糖C2位氨基形成席夫碱以保护氨基, 然后在C6位羟基上接枝2,3-环氧丙基三甲基氯化铵(GTA)季铵盐, 利用稀HCl乙醇溶液脱除席夫碱后合成出O-季铵盐壳聚糖(O-HACC), 再用KIO4将 O-HACC中C2和C3位的部分基团选择性地氧化为醛基, 制备出能与纤维反应结合且具有双重抗菌活性的 O-季铵盐氧化壳聚糖(O-HAOCC), 随后接枝棉织物得到O-HAOCC改性棉织物. 傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)、 氢核磁共振波谱(1H NMR)、 扫描电子显微镜(SEM)和差示扫描量热分析(DSC)等结果表明, O-HAOCC分子中保留了氨基, 同时引入了季铵盐结构和活性醛基, 结晶形态被破坏, 热稳定性降低. 测试结果表明, 氧化3 h的O-HAOCC的水溶性高达237 g/L, 2,2'-联氮双(3-乙基苯并咪唑-6-磺酸)二铵盐(ABTS)自由基清除率在40 min后达到65.58%. 当O-HAOCC质量分数为2%, 反应时间为2 h, 接枝温度为80 ℃时, 改性棉织物的接枝率为9.84%. O-HAOCC改性棉织物对金黄色葡萄球菌和大肠杆菌的抗菌率分别为98.63%和93.38%, 水洗50次后的抗菌率仍在90.75%以上, 可应用于抗菌纺织服装、 家纺面料和医疗卫生品等领域.
中图分类号:
TrendMD:
周晓龙, 汪瑞琪, 陈国丽, 郭文明, 陈飞, 周炎, 孙立德, 汤大保, 许云辉. O-季铵盐氧化壳聚糖的合成及对棉织物的抗菌整理. 高等学校化学学报, 2024, 45(3): 20230375.
ZHOU Xiaolong, WANG Ruiqi, CHEN Guoli, GUO Wenming, CHEN Fei, ZHOU Yan, SUN Lide, TANG Dabao, XU Yunhui. Synthesis of O-quaternary Ammonium Salt-oxidized Chitosan and Its Antibacterial Finishing for Cotton Fabric. Chem. J. Chinese Universities, 2024, 45(3): 20230375.
Fig.1 Effects of different reaction conditions on the degree of substitution of quaternary ammonium salt for chitosan(A) w(NaOH)=0.2%, reaction temperature was 80 ℃, reaction time was 3 h; (B) w(NaOH)=0.2%, n(Schiff-CTS)∶n(GTA)=1∶3, reaction time was 3 h; (C) n(Schiff-CTS)∶n(GTA)=1∶3, reaction temperature was 80 ℃, reaction time was 3 h; (D) w(NaOH)=0.2%, n(Schiff-CTS)∶n(GTA)=1∶3, reaction temperature was 80 ℃.
Fig.3 FTIR spectra of products at each synthesis stage of O⁃HAOCCa. CTS; b. Schiff-CTS; c. Schiff-HACC-0.2-1/3-80-3; d. O-HACC-0.2-1/3-80-3; e. O-HAOCC-4-3.
Fig.4 XRD patterns of products at each synthesis stage of O⁃HAOCCa. CTS; b. Schiff-CTS; c. Schiff-HACC-0.2-1/3-80-3; d. O-HACC-0.2-1/3-80-3; e. O-HAOCC-4-3.
Index | DS of O⁃HACC(%) | Oxidation time of O⁃HAOCC a | ||||||
---|---|---|---|---|---|---|---|---|
34.81 | 58.76 | 75.72 | 86.35 | 1 | 3 | 6 | 8 | |
Water solubility b /(g·L-1) | 26 | 65 | 142 | 176 | 188 | 237 | 279 | 261 |
10‒4 Mvc | 62.7 | 56.8 | 67.2 | 59.1 | 38.5 | 20.3 | 13.7 | 10.4 |
Table 1 Water solubility and molecular weight of O-HACC with different DS and O-HAOCC after oxidation with 4 g/L KIO4 for different time
Index | DS of O⁃HACC(%) | Oxidation time of O⁃HAOCC a | ||||||
---|---|---|---|---|---|---|---|---|
34.81 | 58.76 | 75.72 | 86.35 | 1 | 3 | 6 | 8 | |
Water solubility b /(g·L-1) | 26 | 65 | 142 | 176 | 188 | 237 | 279 | 261 |
10‒4 Mvc | 62.7 | 56.8 | 67.2 | 59.1 | 38.5 | 20.3 | 13.7 | 10.4 |
Fig.8 ABTS·+ radical scavenging activity(A) and UV absorption spectra(B) of ABTS solution after 40 min reaction with CTS(a), O⁃HACC⁃0.2⁃1/3⁃80⁃3(b), O⁃HAOCC⁃4⁃1(c), O⁃HAOCC⁃4⁃3(d) and O⁃HAOCC⁃4⁃6(e)(B) f. control. The inset shows the color change of ABTS·+ solution(f) after 40 min reaction with CTS(a), O-HACC-0.2-1/3-80-3(b), O-HAOCC-4-1(c), O-HAOCC-4-3(d) and O-HAOCC-4-6(e).
Fig.11 SEM images(A1—D1, A2—D2) and EDS analysis(E—H) of cotton fabric(A1, A2, E) and O⁃HAOCC modified cotton fabric with graft ratio of 4.81%(B1, B2, F), 9.84%(C1, C2, G) and 10.95%(D1, D2, H)
Sample | Graft ratio(%) | Breaking strength/N | Capillary effect/(cm·30 min‒1) | Whiteness(%) | Wrinkle recovery angle/(°) |
---|---|---|---|---|---|
Origin cotton fabric | 0 | 423.68 | 8.79 | 81.61 | 124.22 |
Modified cotton fabric | 4.81 | 447.15 | 10.84 | 70.29 | 140.62 |
Modified cotton fabric | 9.84 | 478.23 | 12.01 | 63.34 | 167.28 |
Table 2 Changes in wearability of O-HAOCC modified cotton fabric
Sample | Graft ratio(%) | Breaking strength/N | Capillary effect/(cm·30 min‒1) | Whiteness(%) | Wrinkle recovery angle/(°) |
---|---|---|---|---|---|
Origin cotton fabric | 0 | 423.68 | 8.79 | 81.61 | 124.22 |
Modified cotton fabric | 4.81 | 447.15 | 10.84 | 70.29 | 140.62 |
Modified cotton fabric | 9.84 | 478.23 | 12.01 | 63.34 | 167.28 |
Wearability | Modified cotton fabric with graft ratio of 9.84% | Ref.[ | Ref.[ |
---|---|---|---|
Improvement effect of breaking strength | 12.88% | -2.77% | — |
Improvement effect of wrinkle recovery angle | 34.66% | 31.07% | — |
Improvement effect of capillary effect | 36.63% | — | — |
Antibacterial rate(Antibacterial durability against laundry) | ≥93.38%(≥90.76%) | — | — |
Table 3 The wearability of different materials
Wearability | Modified cotton fabric with graft ratio of 9.84% | Ref.[ | Ref.[ |
---|---|---|---|
Improvement effect of breaking strength | 12.88% | -2.77% | — |
Improvement effect of wrinkle recovery angle | 34.66% | 31.07% | — |
Improvement effect of capillary effect | 36.63% | — | — |
Antibacterial rate(Antibacterial durability against laundry) | ≥93.38%(≥90.76%) | — | — |
Number of washing time | ||||||
---|---|---|---|---|---|---|
Sample | 0 | 20 | 50 | |||
S. aureus | E. coli | S. aureus | E. coli | S. aureus | E. coli | |
Raw cotton fabric | 2.16×106(0) | 4.29×106(0) | — | — | — | — |
Modified cotton fabric with graft ratio of 4.81% | 1.28×105(94.07) | 3.32×105(92.26) | 1.72×105(92.04) | 3.96×105(90.77) | 2.07×105(90.42) | 4.62×105(89.23) |
Modified cotton fabric with graft ratio of 9.84% | 2.96×104(98.63) | 2.84×105(93.38) | 1.06×105(95.09) | 3.55×105(91.72) | 1.33×105(93.86) | 3.96×105(90.76) |
Table 4 Survival colony count(CFU/mL) and antibacterial rate(%, in parentheses) of cotton fabric before and after O-HAOCC modification
Number of washing time | ||||||
---|---|---|---|---|---|---|
Sample | 0 | 20 | 50 | |||
S. aureus | E. coli | S. aureus | E. coli | S. aureus | E. coli | |
Raw cotton fabric | 2.16×106(0) | 4.29×106(0) | — | — | — | — |
Modified cotton fabric with graft ratio of 4.81% | 1.28×105(94.07) | 3.32×105(92.26) | 1.72×105(92.04) | 3.96×105(90.77) | 2.07×105(90.42) | 4.62×105(89.23) |
Modified cotton fabric with graft ratio of 9.84% | 2.96×104(98.63) | 2.84×105(93.38) | 1.06×105(95.09) | 3.55×105(91.72) | 1.33×105(93.86) | 3.96×105(90.76) |
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