Synthesis and properties of poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid conductive interpenetrated hydrogel induced by bovine serum albumin
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摘要: 由于具有优异的导电性、生物相容性、柔韧性和稳定性,聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)导电水凝胶被广泛用于生物传感、神经电极及可穿戴电子等领域。但是,目前合成PEDOT:PSS导电水凝胶大都是通过大幅增加离子强度和降低pH改变PEDOT:PSS的聚集状态使其成胶,条件较苛刻。本文发现一种温和的PEDOT:PSS成胶方法,即通过对牛血清白蛋白(BSA)进行解折叠,改变空间构象,随后充分暴露的多肽链能够原位诱导PEDOT:PSS一步快速形成PEDOT:PSS/BSA互穿网络导电水凝胶。研究表明,该水凝胶不仅保持了PEDOT:PSS网络优异的导电性,同时解折叠的BSA赋予凝胶优异的溶胀性、力学性能和热性能。水凝胶溶血率均低于5%,表明其具有良好的细胞相容性,同时观察到该互穿凝胶能够在人体皮肤、橡胶、塑料和玻璃等多种基底材料上进行黏附,而且由于网络中大量的非共价键存在,该凝胶展现出优异的自愈合性能。总之,本文提供的PEDOT:PSS/BSA互穿网络水凝胶的制备方法及优异性能使其在可穿戴电子及伤口敷料等领域具有良好的应用前景。
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关键词:
- 牛血清白蛋白 /
- 聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸 /
- 生物相容性 /
- 导电性 /
- 互穿网络水凝胶
Abstract: By virtue of their excellent electrical conductivity, biocompatibility, flexibility and stability, poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS) conductive hydrogels have been widely used in biosensors, neural electrode and wearable bioelectronic devices, etc. However, researchers usually greatly increased ionic strength and lowered pH to change the aggregation state of PEDOT:PSS to synthesize PEDOT:PSS conductive hydrogels and to some extent this synthesis condition was harsh in consideration of its future application. In this paper, we provided a facile way to synthesize this conductive hydrogel, that is, bovine serum albumin (BSA) was introduced to induce PEDOT:PSS in situ by changing its spatial configuration to rapidly form a PEDOT:PSS/BSA interpenetrating network conductive hydrogel in one step. It was found that the hydrogel has inherited excellent electrical conductivity of PEDOT:PSS, and in the same time, the unfolded BSA endowed the hydrogel with good swelling and thermal properties. Moreover, the hydrogel has certain mechanical properties and excellent hemolysis rate. To our surprise, the hydrogel also exhibited good adhesion, and self-healing properties. In all, the synthesized method and excellent properties of PEDOT:PSS/BSA interpenetrated hydrogel we provided could have a wide potential in wearable bioelectronics and wound healing dressings. -
图 1 (a) PEDOT:PSS/BSA导电水凝胶制备示意图;(b) 不同BSA浓度的成胶时间;(c) 不同原料含量的成胶示意图(左列:表2编号b和h;中间:表2编号e、f、g;右列:表2编号a、b、c、d、e)
Figure 1. (a) Schematic diagram of the preparation of PEDOT:PSS/BSA conductive hydrogels; (b) Gel formation time at different BSA concentrations; (c) Schematic diagram of gel formation with different raw material contents ( Left column: Numbers b and h from Table 2; Middle: Numbers e, f, g in Table 2; Right column: numbers a, b, c, d, e from Table 2)
TCEP—Tri(2-carboxyethyl) phosphine
图 3 (a) 不同BSA含量PEDOT:PSS/BSA导电水凝胶的流变行为;(b) 不同BSA含量PEDOT:PSS/BSA导电水凝胶的TG曲线(插图是DTG曲线)
Figure 3. (a) Rheological behavior of PEDOT:PSS/BSA conductive hydrogels with different BSA contents; (b) TG curves of PEDOT:PSS/BSA conductive hydrogels with different BSA contents (Illustration is the DTG curves)
G'—Storage modulus; G''—Loss modulus; a—Pure PEDOT:PSS gel; b—PEDOT:PSS/BSA1 gel; c—PEDOT:PSS/BSA2 gel; d—PEDOT:PSS/BSA3 gel
图 6 (a) 不同BSA含量的PEDOT:PSS/BSA导电水凝胶在不同浸泡时间下的溶胀度;(b) 不同BSA含量的PEDOT:PSS/BSA导电水凝胶的饱和溶胀度
Figure 6. (a) Swelling degree of PEDOT:PSS/BSA conductive hydrogels with different BSA contents under different soaking time; (b) Saturated swelling degree of PEDOT:PSS/BSA conductive hydrogels with different BSA contents
图 7 (a) PEDOT:PSS/BSA导电水凝胶良好的柔韧性使它被压缩变形后而不断裂;(b) 不同BSA含量的PEDOT:PSS/BSA导电水凝胶的压缩应力应变曲线
Figure 7. (a) Good flexibility of PEDOT:PSS/BSA conductive hydrogels allows it to be compressed and deformed without breaking; (b) Compressive stress-strain curves of PEDOT:PSS/BSA conductive hydrogels with different BSA contents
图 8 不同BSA含量PEDOT:PSS/BSA导电水凝胶的溶血效果图 (a) 和溶血率 (b)
Figure 8. Hemolysis effect chart (a) and hemolysis rate (b) of PEDOT:PSS/BSA conductive hydrogels with different BSA content
NC—Negative control group; PC—Positive control group; 1#—Pure PEDOT:PSS gel; 2#—PEDOT:PSS/BSA1 gel; 3#—PEDOT:PSS/BSA2 gel; 4#—PEDOT:PSS/BSA3 gel
表 1 聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)/牛血清白蛋白(BSA)导电水凝胶的命名
Table 1. Naming of poly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDOT:PSS)/bovine serum albumin (BSA) conductive hydrogels
Sample BSA
content/
(mg·mL−1)DBSA/μL PEDOT:
PSS/mLPEDOT:PSS — 40 1 PEDOT:PSS/BSA1 40 — 1 PEDOT:PSS/BSA2 70 — 1 PEDOT:PSS/BSA3 100 — 1 Note: DBSA—Dodecylbenzene sulfonic acid. 表 2 导电水凝胶PEDOT:PSS/BSA的配方
Table 2. Formulation of conductive hydrogel of PEDOT:PSS/BSA
Number Solvent system BSA/(mg·mL−1) Urea/(mg·mL−1) TCEP/(mg·mL−1) a PEDOT:PSS 15 540 3 b PEDOT:PSS 20 540 3 c PEDOT:PSS 40 540 3 d PEDOT:PSS 70 540 3 e PEDOT:PSS 100 540 3 f PEDOT:PSS 100 540 0 g PEDOT:PSS 100 0 3 h Water 20 540 3 -
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