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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

谷娜, 王田田, 李红, 等. 活性氯改性锆基MOF复合材料用于高效抑菌[J]. 复合材料学报, 2023, 40(10): 5760-5771. doi: 10.13801/j.cnki.fhclxb.20230104.001
引用本文: 谷娜, 王田田, 李红, 等. 活性氯改性锆基MOF复合材料用于高效抑菌[J]. 复合材料学报, 2023, 40(10): 5760-5771. doi: 10.13801/j.cnki.fhclxb.20230104.001
GU Na, WANG Tiantian, LI Hong, et al. Activated chlorine-modified zirconium-based MOF composites for efficient bacterial inhibition[J]. Acta Materiae Compositae Sinica, 2023, 40(10): 5760-5771. doi: 10.13801/j.cnki.fhclxb.20230104.001
Citation: GU Na, WANG Tiantian, LI Hong, et al. Activated chlorine-modified zirconium-based MOF composites for efficient bacterial inhibition[J]. Acta Materiae Compositae Sinica, 2023, 40(10): 5760-5771. 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
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

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

  • 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。

     

  • 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

    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

    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)

    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

    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

    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))

    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))

    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))

    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

    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

    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

    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

    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

    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

    表  1  皮肤刺激性反应评分标准

    Table  1.   Skin irritation response scoring criteria

    ErythemaScoreEdemaScore
    No0No0
    Mildly (barely visible)1Mildly (barely visible)1
    Moderately (clearly visible)2Moderately (visible bulge)2
    Severely3Severely (skin augmentation of 1 mm, clear contours)3
    下载: 导出CSV

    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%
    11∶346.65
    21∶549.35
    31∶747.12
    41∶949.04
    51∶50.54.85
    61∶528.40
    71∶549.11
    81∶568.54
    下载: 导出CSV

    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)

    StrainsFactorsDiameter/mm
    0 d5 d10 d15 d20 d25 d30 d
    Staphylococcus aureusHigh temperature10.12±0.319.57±0.299.13±0.378.76±0.348.04±0.417.69±0.297.25±0.38
    High humidity10.33±0.289.88±0.349.32±0.148.94±0.258.25±0.187.91±0.437.63±0.36
    Bright light10.14±0.199.62±0.169.17±0.218.82±0.328.15±0.287.83±0.377.33±0.45
    Escherichia coliHigh temperature10.07±0.279.61±0.379.05±0.358.62±0.288.01±0.327.52±0.477.16±0.39
    High humidity10.21±0.249.82±0.299.14±0.368.77±0.358.19±0.277.74±0.427.33±0.32
    Bright light10.11±0.329.67±0.269.09±0.428.53±0.298.08±0.367.67±0.517.25±0.43
    下载: 导出CSV

    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

    StrainsSampleDiameter/mm
    200 mg/L300 mg/L400 mg/L500 mg/L600 mg/L
    Staphylococcus aureusUiO-66-NHCl7.88±0.488.55±0.558.96±0.329.58±0.3210.03±0.41
    UiO-66-NH200000
    Escherichia coliUiO-66-NHCl7.94±0.518.27±0.438.73±0.239.21±0.189.98±0.34
    UiO-66-NH200000
    下载: 导出CSV

    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/dComplete skin group (Score)Damaged skin group (Score)
    UiO-66-NHClWaterUiO-66-NHClWater
    10000
    20000
    30000
    40000
    50000
    60000
    70000
    下载: 导出CSV
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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

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