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，有望制备具有良好力学性能的抗菌水凝胶，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。本文首先以2, 2, 6, 6-四甲基哌啶氧化物(TEMPO)氧化纳米纤维素(TOCNF)为复合基材，AgNO3为银源，通过水热法原位复合制备Ag-CNF复合材料。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，并将Ag-CNF/PAM 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。Ag-CNF/PAM 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 (CNF) 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 CNF 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, Ag-CNF composites were in situ synthesized using 2, 2, 6, 6-tetramethylpiperidoxyl (TEMPO)-oxidized CNF (TOCNF) as a composite substrate and 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 with good tensile properties, adhesion, antibacterial properties, and UV-shielding properties. The Ag-CNF/PAM hydrogels were then packaged into a strain-responsive sensor. The electrical and sensing properties were studied. Ag-CNF/PAM 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:
- CNF /
- AgNPs /
- hydrogel /
- antibacterial /
- strain-responsive sensor
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图 1 AgNO3、TEMPO氧化纳米纤维素(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
TEMPO—2, 2, 6, 6-tetramethylpiperidoxyl
图 2 TOCNF (a)和 Ag-CNF (b)的 AFM 图像以及 TOCNF 长度统计(c)和纳米银颗粒(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 silver nanoparticles (AgNPs) (d)
d10, d50, d90— TOCNF with length less than 87.6 nm, 150.0 nm and 218.6 nm accounted for 10%, 50% and 90% of the total amount in the sample
图 3 聚丙烯酰胺(PAM)和Ag-CNF/PAM水凝胶的制备示意图
Figure 3. Schematic representation of the preparation of polyacrylamide (PAM) and Ag-CNF/PAM hydrogels
APS—Ammonium persulphate; MBA—N, N'-methylene diacrylamide; TA—Tannic acid; AgNPs—Ag nanoparticles
图 4 Ag-CNF/PAM 水凝胶(a)、扭转(b)、打结(c)以及承重(d)的实物图
Figure 4. Real photos of Ag-CNF/PAM hydrogel (a), twisting (b), knotting (c), and bearing (d)
图 5 TOCNF、AM、TA、PAM 和 Ag-CNF/PAM 水凝胶红外图谱
Figure 5. FTIR spectra of TOCNF, AM, TA, PAM and Ag-CNF/PAM hydrogels
图 6 Ag-CNF/PAM 水凝胶的表面((a), (b))和横截面((c), (d))的 SEM 图像
Figure 6. SEM images of surface ((a), (b)) and cross-sections ((c), (d)) of Ag-CNF/PAM hydrogels
图 7 Ag-CNF/PAM 水凝胶对不同基材的粘附图片
Figure 7. Photos of Ag-CNF/PAM hydrogel adhesion to different substrates
图 8 不同AM含量和TA含量的 Ag-CNF/PAM 水凝胶对纸张的粘附剪切应力对比
Figure 8. Comparison of adhesive shear stress of Ag-CNF/PAM hydrogels with different AM and TA contents
图 9 Ag-CNF/PAM 水凝胶对不同基底的重复粘附测试
Figure 9. Repeated adhesion test of Ag-CNF/PAM hydrogel to different substrates
图 10 不同TA含量的 Ag-CNF/PAM 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 Ag-CNF/PAM hydrogels with different TA contents
图 11 Ag-CNF/PAM 水凝胶对大肠杆菌(E. coli)和金黄色葡萄球菌(S. aureus)的接触抗菌效果
Figure 11. Contact antibacterial effect of Ag-CNF/PAM hydrogels on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus)
图 12 PAM 和 Ag-CNF/PAM 水凝胶的 UV-vis 透射率光谱
Figure 12. UV-vis transparent spectra of PAM and Ag-CNF/PAM hydrogels
图 13 ((a), (b))基于Ag-CNF/PAM水凝胶的应变响应传感器在不同应变(0%~500%)下的相对电阻变化(ΔR/R0)；(c) 应变响应传感器的应变系数(GF)
Figure 13. ((a), (b)) Changes in the relative resistance (ΔR/R0) of Ag-CNF/PAM hydrogel-based strain-responsive sensors at different strains (0%-500%); (c) Gauge factor (GF) of the strain-response sensors
图 14 基于 Ag-CNF/PAM 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 Ag-CNF/PAM hydrogel-based strain-responsive sensors during 100% strain cyclic loading-unloading
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