Preparation of electrospun composite fibers functionalized with an iron complex and their CO-release behavior
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摘要: CO缓释材料对CO药用价值研究具有重要意义。本文以二甲基乙酰胺、丙酮为溶剂,铁化合物[Fe(η5-Cp)(CO)2I]为铁基一氧化碳释放剂(FeCORM),醋酸纤维素(CA)、聚乙烯吡咯烷酮(PVP)为基体聚合物,通过静电纺丝技术制备了不同FeCORM含量的微纳米复合纤维材料,并通过ATR-FTIR、UV-vis DRS、SEM等技术对有关材料进行了表征。研究了这些材料在不同光源(蓝、绿、红)照射下CO释放行为,分析了其CO释放动力学,并定量分析了不同材料释放CO的量。结果表明:复合纤维材料释放CO的速率与FeCORM含量及光源波长有关,一般含量越低、波长越短则释放速率越快;其释放过程符合一级动力学模型,表观速率常数(kobs)在1.59~0.11 min−1之间、半衰期t1/2在0.4~6.3 min左右。复合纤维材料释放CO的剂量y与FeCORM的质量百分含量x间呈良好线性依赖关系,满足方程式y=0.0284x−0.0158。Abstract: CO-releasing materials are valuable for CO medicinal applications. Herein, by using an iron complex, [Fe(η5-Cp)(CO)2I] as iron-based carbon monoxide-releasing molecule (FeCORM), cellulose acetate (CA) and polyvinylpyrrolidone (PVP) as matrix polymers, CA-PVP-based composite fibers with various amounts of FeCORM were prepared via electrospinning technology in a mixture solution of dimethylacetamide/acetone. The composite fibers were characterized by means of ATR-FTIR, UV-vis DRS, SEM techniques. CO-releasing performance of the composite fibers was then investigated upon irradiation of blue/green/red lights, and their corresponding kinetic data were obtained, respectively. The amounts of CO released by the composite fibers were further quantified. Our results demonstrate that the rates of CO-release for the composite fibers are depending on both the contents of FeCORM and the wavelengths of the light sources. Generally, the lower the content and the shorter the wavelength, the faster the release rate should be. Additionally, first-order kinetics are assigned to the CO-release process of the composite fibers, with a rate constant kobs between 1.59-0.11 min−1, and a half-life t1/2 between 0.4-6.3 min, respectively. Furthermore, a satisfied linear-relationship is estimated between the dose of released CO for the composite fibers y and the mass percentage of FeCORM x with the equation following: y=0.0284x−0.0158.
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Key words:
- carbon monoxide /
- iron carbonyls /
- electrospinning /
- cellulose acetate /
- polyvinylpyrrolidone /
- composite fiber /
- photoinduction
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表 1 不同铁基一氧化碳释放剂(FeCORM)含量纺丝溶液的组成
Table 1. Electrospun solutions component with different iron-based carbon monoxide-releasing molecule (FeCORM) contents
Material CA/
mgPVP/
mgDMAC/
mLACT/
mLFeCORM/
mgCA-PVP 240 80 1.0 2.0 0 10FeCORM/CA-PVP 240 80 1.0 2.0 10 20FeCORM/CA-PVP 240 80 1.0 2.0 20 30FeCORM/CA-PVP 240 80 1.0 2.0 30 40FeCORM/CA-PVP 240 80 1.0 2.0 40 50FeCORM/CA-PVP 240 80 1.0 2.0 50 Notes: CA—Cellulose acetate; PVP—Polyvinyl pyrrolidone; DMAC—Dimehyl acetamide; ACT—Acetone. 表 2 FeCORM/醋酸纤维素(CA)-聚乙烯吡咯烷酮(PVP)复合纤维材料静电纺丝参数
Table 2. Parameters of the electrospinning of FeCORM/cellulose acetate (CA)-polyvinylpyrrolidone (PVP) composite fibers
Material Voltage/
kVRate/
(μm·s−1)Temperature/
°CHumidity/
%CA-PVP 15.00 0.5 21.3 40 10FeCORM/
CA-PVP15.04 0.5 22.3 41 20FeCORM/
CA-PVP15.05 0.5 20.2 42 30FeCORM/
CA-PVP15.10 0.4 21.3 48 40FeCORM/
CA-PVP15.10 0.4 20.3 42 50FeCORM/
CA-PVP15.10 0.4 21.1 41 表 3 FeCORM/CA-PVP复合纤维材料在不同波长光诱导下CO释放动力学数据
Table 3. Kinetic data of FeCORM/CA-PVP composite fibers upon irradiation of lights with different wavelengths
Material kobs/min−1 t1/2/min Blue Green Red Blue Green Red 10FeCORM/CA-PVP 1.59 0.41 0.12 0.4 1.7 5.8 20FeCORM/CA-PVP 0.95 0.36 0.11 0.7 1.9 6.3 30FeCORM/CA-PVP 0.71 0.29 0.12 1.0 2.4 5.8 40FeCORM/CA-PVP 0.57 0.24 0.11 1.2 2.9 6.3 50FeCORM/CA-PVP 0.40 0.23 0.11 1.7 3.0 6.3 Notes: kobs—Observed rate constant; t1/2—Halftime. -
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