Silver nanoparticle/nanocellulose composites antibacterial strain-responsive hydrogels
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摘要: 基于纳米银颗粒(AgNPs)的抗菌导电水凝胶在可穿戴设备、电子皮肤、生物传感器等领域有重要应用，其绿色制造是目前的研究热点之一。纳米纤维素(CNF)因其独特的物理化学性质，在智能水凝胶的制备与应用中得到越来越多的关注。将 AgNPs 与 CNF 复合并应用到水凝胶中，有望制备具有良好机械性能的抗菌水凝胶，对水凝胶在智能可穿戴领域中的应用具有重要的指导意义。本研究首先以羧基改性的纳米纤维素(TOCNF)为复合基材，硝酸银(AgNO3)为银源，通过水热法原位复合制备纳米银/纳米纤维素复合材料(Ag-CNF)。随后，将 Ag-CNF 和 单宁酸(TA) 作为功能性添加剂引入聚丙烯酰胺(PAM)水凝胶中，制备了具有良好拉伸性能、粘附性、抗菌性和紫外屏蔽性的 Ag-CNF/PAM 水凝胶(AP 水凝胶)，并将 AP 水凝胶封装制备成应变响应传感设备，研究其电学和传感性能。AP 水凝胶在 100% 的应变循环下能够保持稳定重复的电信号输出，也能够用于手腕动作和头部动作的动作检测，在应变响应传感领域具有良好的应用前景。Abstract: The antibacterial and conductive hydrogels based on silver nanoparticles (AgNPs) have important applications in wearable devices, electronic skin, biosensors, and other areas, and their green manufacturing is currently the focus of much research. Nanocellulose has attracted more attention relating to the preparation and application of the smart hydrogels due to its unique physico-chemical properties. When AgNPs are combined with nanocellulose and applied to hydrogels, it is expected to lead to fabrication of antibacterial hydrogels with good mechanical properties, which has guiding significance for the application of hydrogels in the area of intelligent wearable systems. In the present study, AgNPs/nanocellulose composites (Ag-CNF) were in situ synthesized using TEMPO-oxidized nanocellulose (TOCNF) as a composite substrate and silver nitrate (AgNO3) as a source of silver. Ag-CNF and tannic acid (TA) were introduced to polyacrylamide (PAM) hydrogels as functional additives to prepare the Ag-CNF/PAM hydrogel (AP hydrogel) with good tensile properties, adhesion, antibacterial properties, and UV-shielding properties. The AP hydrogels were then packaged into a strain-responsive sensor. The electrical and sensing properties were studied. AP hydrogels can maintain stable and repeated electrical output under 100% strain cycle and can also be used for wrist motion and head motion detection, which has potential for use as a strain-responsive sensor.
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Key words:
- nanocellulose /
- silver nanoparticle /
- hydrogel /
- antibacterial /
- strain-responsive sensor
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图 1 AgNO3、羧基改性的纳米纤维素(TOCNF)、AgNO3-TOCNF和 Ag-CNF 的 UV-vis 吸收光谱
Figure 1. Absorption spectra of AgNO3 solution, TEMPO-oxidized nanocellulose (TOCNF), AgNO3-TOCNF and Ag-CNF
图 2 TOCNF(a)和 Ag-CNF(b)的 AFM 图像以及 TOCNF 长度统计(c)和 AgNPs 的粒径统计(d)
Figure 2. AFM images of TOCNF (a) and Ag-CNF (b), the length statistic of TOCNF (c) and the particle size statistics of AgNPs(d)
图 3 聚丙烯酰胺(PAM)和 AP (Ag-CNF/PAM)水凝胶的制备示意图
Figure 3. Schematic representation of the preparation of polyacrylamide (PAM) and AP (Ag-CNF/PAM) hydrogels
图 4 AP 水凝胶(a)扭转(b)、打结(c)以及承重(d)的实物图
Figure 4. Real picture of AP hydrogel (a) twisting (b), knotting (c), and bearing (d)
图 5 TOCNF，AM、TA、PAM 和 AP 水凝胶红外谱图
Figure 5. FTIR spectrums of TOCNF, AM, TA, PAM and AP hydrogels
图 6 AP 水凝胶的表面(a, b)和横截面(c, d)的 SEM 图片
Figure 6. SEM images of surface (a, b) and cross-sections (c, d) of AP hydrogels
图 8 不同 AM 含量和 TA 含量的 AP 水凝胶对纸张的粘附剪切应力对比
Figure 8. Comparison of adhesive shear stress of AP hydrogels with different AM and TA contents on paper
图 9 AP 水凝胶对不同基底的重复粘附测试
Figure 9. Repeated adhesion test of AP hydrogel to different substrates
图 10 不同 单宁酸(TA) 含量的 AP 水凝胶的应力-应变曲线(a)和对应的性能参数(b)
Figure 10. Stress-strain curves (a) and corresponding performance parameters (b) of AP hydrogels with different tannic acid (TA) contents
图 11 AP 水凝胶对大肠杆菌和金黄色葡萄球菌的接触抗菌效果
Figure 11. Contact antibacterial effect of AP hydrogels on E. coli and S. aureus
图 12 PAM 和 AP 水凝胶的 UV-vis 透射率光谱
Figure 12. The UV-vis transparent spectrum of PAM and AP hydrogels
图 13 基于 AP 水凝胶的应变响应传感器在不同应变(0-500%)下(a, b)的相对电阻变化；应变响应传感器的应变系数(c)
Figure 13. Changes in the relative resistance of AP hydrogel-based strain-responsive sensors at different strains (0-500%) (a, b); gauge factor of the strain-response sensors (c)
图 14 基于 AP 水凝胶的应变响应传感器在 100%应变循环加载-卸载过程中的相对电阻变化
Figure 14. Changes in relative resistance of AP hydrogel-based strain-responsive sensors during 100% strain cyclic loading-unloading
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