活性氯改性锆基MOF复合材料用于高效抑菌

谷娜; 王田田; 李红; 任伟杰; 董倩茹; 高金龙

doi:10.13801/j.cnki.fhclxb.20230104.001

活性氯改性锆基MOF复合材料用于高效抑菌

doi: 10.13801/j.cnki.fhclxb.20230104.001

1.
河北科技大学　化学与制药工程学院，石家庄 050018
2.
河北科技大学　理学院，石家庄 050018

详细信息

通讯作者:
高金龙，硕士，副教授，硕士生导师，研究方向为载药纳米材料和水环境污染功能材料　E-mail: 841230252@qq.com

中图分类号: TQ134.1
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- 被引次数: 0
出版历程
- 收稿日期: 2022-10-25
- 修回日期: 2022-12-05
- 录用日期: 2022-12-22
- 网络出版日期: 2023-01-04
- 刊出日期: 2023-10-15

Activated chlorine-modified zirconium-based MOF composites for efficient bacterial inhibition

1.
School of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
2.
School of Science, Hebei University of Science and Technology, Shijiazhuang 050018, China

摘要

摘要: 近年来，工业化污染严重导致各类细菌滋生，致病性细菌感染可通过各种方式进行快速传播，存在很大的感染风险。因此，开发高性能的抑菌材料并研究其抑菌机制具有重要的应用价值。为了解决这一问题，本文设计通过亚氯酸钠溶液改性锆基金属-有机骨架材料UiO-66-NH₂，制备了一种新型纳米复合抑菌材料UiO-66-NHCl，采用XRD、FTIR、SEM、TEM、EDS和XPS等对金属-有机骨架(MOF)复合材料结构和化学组成进行表征，同时探索不同负载工艺对氯负载量的影响，并对UiO-66-NHCl复合材料的抑菌性能及皮肤刺激性实验进行研究。结果表明：通过浸渍键合的方法在UiO-66-NH₂上引入了活性氯，改变UiO-66-NH₂在NaClO₂溶液中的氯负载比例(质量比m(UiO-66-NH₂)∶m(NaClO₂))和氯化时间可以提高氯负载量，当氯负载比例为1∶5、氯化时间为4 h时，氯负载量最高；在高温、高湿和强光等条件下，仍能保持其原始氯负载量的80%，有较好的稳定性。抑菌活性表明，相比于原始UiO-66-NH₂材料，UiO-66-NHCl复合材料对金黄色葡萄球菌和大肠杆菌均有抑制作用，氯含量较高的样品显示出较高的抑菌效果，且无刺激性。
- 金属-有机骨架 /
- 亚氯酸钠 /
- 改性 /
- 稳定性 /
- 抑菌
Abstract: In recent years, serious industrial pollution has led to the growth of various types of bacteria, and pathogenic bacterial infections can be spread rapidly by various means, posing a great risk of infection. Therefore, it is important to develop high-performance antibacterial materials and study their antibacterial mechanisms for application. To address this issue, this work designed a novel nanocomposite bacteriostatic material UiO-66-NHCl by modifying zirconium-based metal-organic backbone material UiO-66-NH₂ via sodium chlorite solution, and characterized the structure and chemical composition of metal-organic framework (MOF) composites by using XRD, FTIR, SEM, TEM, EDS and XPS, and the effects of different loading processes on the chlorine loading were also explored, and the antibacterial properties and skin irritation experiments of UiO-66-NHCl composites were investigated. The results show that the active chlorine is introduced on UiO-66-NH₂ by impregnation bonding, and the chlorine loading can be increased by changing the chlorine loading ratio (mass ratios m(UiO-66-NH₂)∶m(NaClO₂)) and chlorination time of UiO-66-NH₂ in NaClO₂ solution, and the highest chlorine loading is achieved when the chlorine loading ratio is 1∶5 and the chlorination time is 4 h. Under the conditions of high temperature, high humidity and high temperature, it can still maintain 80% of its original chlorine loading and has good stability. The inhibition activity show that the UiO-66-NHCl composites inhibit both Staphylococcus aureus and Escherichia coli compared to the original UiO-66-NH₂ material, and the samples with higher chlorine content show higher inhibition effect and no irritation.
- metal-organic framework /
- sodium hypochlorite /
- modified /
- stability /
- antibacterial

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图 1 UiO-66-NH₂和UiO-66-NHCl的XRD图谱：(a) 不同氯负载比例；(b) 不同氯化时间

Figure 1. XRD patterns of UiO-66-NH₂和UiO-66-NHCl: (a) Different chlorine loading ratios; (b) Different chlorination time

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图 2 UiO-66-NH₂/NaClO₂的SEM图像：((a)~(d)) 负载比例分别为1∶3、1∶5、1∶7、1∶9；((e)~(h)) 氯化时间分别为0.5 h、2 h、4 h、6 h

Figure 2. SEM images of UiO-66-NH₂/NaClO₂: ((a)-(d)) Loading ratios of 1∶3, 1∶5, 1∶7, 1∶9; ((e)-(h)) Chlorination time of 0.5 h, 2 h, 4 h, 6 h, respectively

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图 3 UiO-66-NH₂加KI溶液(左)；UiO-66-NHCl加KI溶液(中)；UiO-66-NHCl加KI溶液后滴定(右)

Figure 3. KI solution added to UiO-66-NH₂ (left); KI solution added to UiO-66-NHCl (middle); KI solution added to UiO-66-NHCl after titration (right)

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图 4 UiO-66-NH₂和UiO-66-NHCl的XRD图谱

Figure 4. XRD patterns of UiO-66-NH₂ and UiO-66-NHCl

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图 5 UiO-66-NH₂和UiO-66-NHCl的FTIR图谱

Figure 5. FTIR spectra of UiO-66-NH₂ and UiO-66-NHCl

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图 6 UiO-66-NH₂ ((a)~(c))和UiO-66-NHCl ((d)~(f))的SEM图像

Figure 6. SEM images of UiO-66-NH₂ ((a)-(c)) and UiO-66-NHCl ((d)-(f))

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图 7 UiO-66-NH₂ ((a)~(c))和UiO-66-NHCl ((d)~(f))的TEM图像

Figure 7. TEM images of UiO-66-NH₂ ((a)-(c)) and UiO-66-NHCl ((d)-(f))

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图 8 UiO-66-NH₂和UiO-66-NHCl的EDS元素分析((a), (b))；UiO-66-NHCl的元素分布图像((c)~(f))

Figure 8. EDS elemental analysis of UiO-66-NH₂ and UiO-66-NHCl ((a), (b)); Elemental distribution images of UiO-66-NHCl ((c)-(f))

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图 9 (a) UiO-66-NH₂和UiO-66-NHCl的XPS全谱图；(b) C1s；(c) O1s；(d) Zr3d；(e) N1s；(f) Cl2p

Figure 9. (a) Total XPS spectra of UiO-66-NH₂ and UiO-66-NHCl; (b) C1s; (c) O1s; (d) Zr3d; (e) N1s; (f) Cl2p

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图 10 UiO-66-NHCl在不同条件下的稳定性实验结果

Figure 10. Experimental results on the stability of UiO-66-NHCl under different conditions

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图 11 UiO-66-NHCl复合材料对金黄色葡萄球菌的抑菌效果

Figure 11. Bacterial inhibition effect of UiO-66-NHCl composite against Staphylococcus aureus

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图 12 UiO-66-NHCl复合材料对大肠杆菌的抑菌效果

Figure 12. Bacterial inhibition effect of UiO-66-NHCl composites on Escherichia coli

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图 13 UiO-66-NH₂材料改性前后对金黄色葡萄球菌的抑菌结果影响

Figure 13. Effect of inhibition results of UiO-66-NH₂ material on Staphylococcus aureus before and after modification

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图 14 UiO-66-NH₂材料改性前后对大肠杆菌的抑菌结果影响

Figure 14. Effect of inhibition results of UiO-66-NH₂ material on Escherichia coli before and after modification

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表 1 皮肤刺激性反应评分标准

Table 1. Skin irritation response scoring criteria

Erythema	Score	Edema	Score
No	0	No	0
Mildly (barely visible)	1	Mildly (barely visible)	1
Moderately (clearly visible)	2	Moderately (visible bulge)	2
Severely	3	Severely (skin augmentation of 1 mm, clear contours)	3

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表 2 活性氯负载比例与氯化时间对氯负载量的影响

Table 2. Effect of active chlorine loading ratio and chlorination time on chlorine loading

No.	Chlorine load ratio	Chlorination time/h	Chlorine loading/wt%
1	1∶3	4	6.65
2	1∶5	4	9.35
3	1∶7	4	7.12
4	1∶9	4	9.04
5	1∶5	0.5	4.85
6	1∶5	2	8.40
7	1∶5	4	9.11
8	1∶5	6	8.54

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表 3 UiO-66-NHCl复合材料在高温、高湿和强光条件下的抑菌圈直径的影响(标准差，±SD mm)

Table 3. Effect of UiO-66-NHCl composites on the diameter of the inhibition circle under high temperature, high humidity and strong light conditions (Standard deviation, ±SD mm)

Strains	Factors	Diameter/mm
Strains	Factors	0 d	5 d	10 d	15 d	20 d	25 d	30 d
Staphylococcus aureus	High temperature	10.12±0.31	9.57±0.29	9.13±0.37	8.76±0.34	8.04±0.41	7.69±0.29	7.25±0.38
	High humidity	10.33±0.28	9.88±0.34	9.32±0.14	8.94±0.25	8.25±0.18	7.91±0.43	7.63±0.36
	Bright light	10.14±0.19	9.62±0.16	9.17±0.21	8.82±0.32	8.15±0.28	7.83±0.37	7.33±0.45
Escherichia coli	High temperature	10.07±0.27	9.61±0.37	9.05±0.35	8.62±0.28	8.01±0.32	7.52±0.47	7.16±0.39
	High humidity	10.21±0.24	9.82±0.29	9.14±0.36	8.77±0.35	8.19±0.27	7.74±0.42	7.33±0.32
	Bright light	10.11±0.32	9.67±0.26	9.09±0.42	8.53±0.29	8.08±0.36	7.67±0.51	7.25±0.43

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表 4 浓度对UiO-66-NHCl和UiO-66-NH₂材料抑菌圈直径的影响对比(±SD mm)

Table 4. Comparison of the effect of concentration on the diameter of the inhibition circle of UiO-66-NHCl and UiO-66-NH₂

Strains	Sample	Diameter/mm
Strains	Sample	200 mg/L	300 mg/L	400 mg/L	500 mg/L	600 mg/L
Staphylococcus aureus	UiO-66-NHCl	7.88±0.48	8.55±0.55	8.96±0.32	9.58±0.32	10.03±0.41
Staphylococcus aureus	UiO-66-NH₂	0	0	0	0	0
Escherichia coli	UiO-66-NHCl	7.94±0.51	8.27±0.43	8.73±0.23	9.21±0.18	9.98±0.34
Escherichia coli	UiO-66-NH₂	0	0	0	0	0

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表 5 UiO-66-NHCl多次给药皮肤刺激反应实验结果

Table 5. Experimental results of skin irritation response to multiple doses of UiO-66-NHCl

Dosing time/d	Complete skin group (Score)		Damaged skin group (Score)
Dosing time/d	UiO-66-NHCl	Water	UiO-66-NHCl	Water
1	0	0	0	0
2	0	0	0	0
3	0	0	0	0
4	0	0	0	0
5	0	0	0	0
6	0	0	0	0
7	0	0	0	0

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