Preparation of antimicrobial anti-swelling conductive hydrogels based on polyaniline and their applications
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摘要: 导电水凝胶是柔性传感器件理想的候选材料。但在实际应用过程中，导电水凝胶的成本高，力学性能差、传感探测范围有限、功能单一、环保性等问题，严重阻碍了它的实际应用。为了开发一种力学性能优秀、成本低、环保和多功能的，可适用于各种复杂应用环境的导电水凝胶，选用聚乙烯醇(PVA)和导电聚合物聚苯胺(PANI)构成水凝胶主体的双网络结构，植酸(PA)和硼酸(BA)作为交联剂构建一种低成本、环境友好性、高强度和多功能PVA/PANI/PA/BA导电水凝胶。研究了不同配比的PVA/PANI的复合水凝胶的力学性能、微观结构、电化学性能、抗溶胀性和抗菌性等性能，探讨了基于此导电水凝胶制作的传感器的传感性能。研究表明在PVA质量分数15%的复合体系中，此水凝胶兼顾了具有优秀的拉伸强度(断裂应力达357 kPa，断裂形变达504%)、良好的电化学性能(导电率为146 mS/m)、优异的抗溶胀性(浸泡15天溶胀率仅4.56%，对应的断裂强度变化和断裂伸长率变化分别不超过20%和0.1%)和优秀的抗菌性能等多功能，做到了各功能的相互平衡。基于此水凝胶制作的传感器来监测人体实时的运动情况时，能将眉头、手指和手腕运动信号转换成稳定的电信号，可将其应用于电子皮肤和可穿戴传感器等领域。Abstract: Conductive hydrogels are ideal candidates for flexible sensor devices. However, in the practical application process, the high cost of conductive hydrogel, poor mechanical properties, limited sensing detection range, single function, environmental protection, and other issues, seriously hindered its practical application. To develop an electrically conductive hydrogel with excellent mechanical properties, low-cost, environmentally friendly, and multifunctional for a variety of complex application environments, polyvinyl alcohol (PVA) and the conductive polymer polyaniline (PANI) were selected to form a double network structure of the hydrogel body, and phytic acid (PA) and boronic acid (BA) were used as cross-linking agents to construct a low-cost, environmentally friendly, high-strength, and multifunctional PVA/PANI/PA/BA conductive hydrogel. The mechanical properties, microstructure, electrochemical properties, swelling resistance, and antimicrobial properties of composite hydrogels with different ratios of PVA/PANI were investigated, and the sensing performance of sensors based on this conductive hydrogel was discussed. It is shown that in the composite system with 15% PVA mass fraction, this hydrogel has excellent tensile strength (breaking stress up to 357 kPa, deformation at break up to 504%), good electrochemical properties (electrical conductivity of 146 mS/m), excellent resistance to swelling (the swelling rate is only 4.56% for 15 days of immersion, and the changes in breaking strength and elongation at break do not exceed 20% and 0.1%, respectively), and excellent antimicrobial properties, achieving a balance of functions. When sensors made based on this hydrogel are used to monitor the real-time movement of the human body, they can convert brows, finger, and wrist movement signals into stable electrical signals, which can be used in fields such as electronic skin and wearable sensors.
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Key words:
- PVA /
- PANI /
- conductive hydrogels /
- antibiosis /
- sensing performance
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图 1 PNAB水凝胶的(a)制备路线和(b)合成示意图
Figure 1. (a) Preparation route and (b) Synthesis diagram of PNAB hydrogel
图 2 (a) P15NA水凝胶、(b) P15NAB水凝胶、(c) P20NAB水凝胶的SEM图像
Figure 2. SEM images of (a) P15NA hydrogel, (b) P15NAB hydrogel, (c) P20NAB hydrogel
图 3 PNAB水凝胶、PNA水凝胶、PVA/BA水凝胶和PANI/PA的FTIR
Figure 3. FTIR of PNAB hydrogel, PNA hydrogel, PVA/BA hydrogel and PANI/PA
图 4 (a)PxNAB的机械和加工性能；(b)PxNAB的应力-应变曲线
Figure 4. (a) Mechanical and processing properties of PxNAB;(b) Stress-strain curves of PxNAB
图 5 (a) P15NA、P15NAB和P20NAB水凝胶对E.coli(左)和S. aureus(右)的抗菌试验照片；(b)抑制区的环形直径
Figure 5. (a) Antibacterial test photos of P15NA, P15NAB and P20NAB hydrogels against E. coli(left) and S. aureus(right); (b) The circular diameter of the suppression zone
图 6 (a)&(b)浸泡2 h和120 h后水凝胶的溶胀率；(c)&(d)原水凝胶与浸泡15天后的水凝胶的应力和应变的对比
Figure 6. (a)&(b) swelling rate of hydrogel after soaking for 2 h and 120 h; (c)&(d) Comparison of stress and strain of hydrogel and soaked hydrogel for 15 days
图 7 (a) PNAB在简单电路中做导体;(b)PXNAB水凝胶的电导率
Figure 7. (a) PNAB is used as the conductor in simple circuits;(b) Conductivity of PXNAB hydrogel
图 8 (a) PNA与PxNAB水凝胶在10 mV/s扫描速率下的CV图；(b) P15NAB在不同扫描速率下的CV图
Figure 8. (a) CV diagram of PNA and PxNAB hydrogels at a scanning rate of 10 mV/s; (b) CV images of P15NAB at different scanning rates
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