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林业科学 ›› 2020, Vol. 56 ›› Issue (3): 109-116.doi: 10.11707/j.1001-7488.20200312

• 论文与研究报告 • 上一篇    下一篇

酶解木质素质量浓度对纳米木质素粒子结构及载药行为的影响

周宇,韩雁明,李改云,储富祥*   

  1. 中国林业科学研究院木材工业研究所 北京 100091
  • 收稿日期:2018-12-27 出版日期:2020-03-25 发布日期:2020-04-08
  • 通讯作者: 储富祥
  • 基金资助:
    国家自然科学基金项目(31770610)

Effect of Enzymatic Hydrolysis Lignin Mass Concentration on the Structure of Lignin Nano Particles and Drug-Loading Behavior

Yu Zhou,Yanming Han,Gaiyu Li,Fuxiang Chu*   

  1. Research Institute of Wood Industry, CAF Beijing 100091
  • Received:2018-12-27 Online:2020-03-25 Published:2020-04-08
  • Contact: Fuxiang Chu

摘要:

目的: 研究酶解木质素(EHL)在四氢呋喃(THF)中的质量浓度对制备纳米木质素中空粒子(LHNPs)结构的影响以及载盐酸阿霉素(DOX)粒子(DOX@ LHNPs)结构对药物控释行为的影响,为LHNPs在不同领域的选择性包载利用提供参考。方法: 将不同质量EHL溶解在THF中,制备不同质量浓度木质素溶液,向溶液中滴加去离子水使两亲性木质素自组装成结构不同的纳米木质素中空粒子。在制备过程中加入一定质量DOX,EHL自组装成纳米粒子的同时会将DOX包裹在LHNPs腔体内,形成载药纳米粒子。借助透射电镜(TEM)、扫描电镜(SEM)、激光粒度仪(DLS)、比表面与孔隙度分析仪等手段表征材料的微观结构和粒径尺寸。利用紫外-可见光分光光度计(UV-vis)、X射线衍射仪(XRD)、红外光谱仪(FTIR)等仪器表征测试LHNPs对DOX的包载和控释。结果: DLS测试结果表明,EHL初始质量浓度从0.3 mg·mL-1增加到3 mg·mL-1,颗粒直径从552.6 nm减小到266.8 nm,PDI基本保持稳定;制备的纳米木质素粒子尺寸分布均匀,可在水中稳定保存10天以上。利用TEM、SEM结合比表面与孔隙度分析可知,纳米木质素粒子呈中空球形结构,表面开孔;随着EHL初始质量浓度增加,粒子的直径、表面积和孔隙体积均有所减小。UV-vis、XRD、FTIR表征测试表明,LHNPs能够包载DOX。酸性(pH=5.5)条件下,自由DOX和载药粒子释放DOX的速度均大于中性(pH=7.4)条件下的药物释放速度。较大的比表面积和孔隙率可提高纳米中空粒子对DOX的包载能力,壳层更厚的粒子对DOX拥有更稳定的控释能力。结论: 酶解木质素可自组装成尺寸稳定且表面具有单孔的纳米级中空球形粒子。控制酶解木质素初始质量浓度,可调节中空粒子的直径和壳层壁厚。对于DOX@ LHNPs,比表面积和孔隙率越大,其载药量越大,但结构更规整、壳层壁更厚的纳米中空载药粒子对DOX的释放更稳定。

关键词: 酶解木质素, 纳米木质素, 结构, 盐酸阿霉素

Abstract:

Objective: The effects of enzymatic hydrolysis lignin(EHL)mass concentration in tetrahydrofuran(THF)on the structure of lignin hollow nanoparticles(LHNPs)and the effects of the structure of doxorubicin hydrochloride(DOX)loaded LHNPs(DOX@LHNPs)on the drug controlled release behavior were investigated in this study, which might provide bases for selecting entrapment utilization of LHNPs in different fields. Method: LHNPs were prepared with dissolving different quality of EHL in THF and afterward dropping deionized water to the solution. EHL could be self-assembled into nanoparticles and loaded DOX- iniside LHNPs forming drug-loaded nanoparticles, by adding a certain quality of DOX to the mixed solution. The microstructure and particle size of the material were characterized by transmission electron microscope(TEM), scanning electron microscope(SEM), laser particle size analyzer(DLS)and surface area and a pore volume analyzer. Ultraviolet-visible spectrophotometer(UV-vis), X-ray diffractometer(XRD) and infrared spectrometer(FTIR)were performed to quantify the encapsulation and controlled release of DOX by LHNPs. Result: The value obtained by DLS showed that an increase of the pre-dropping lignin mass concentration from 0.3 to 3 mg·mL-1 led to the nanoparticles size decreased from 552.6 to 266.8 nm, whereas the PDI values were basically stable. Additionally, the distribution for size of nanoparticles was uniform, which could be stored in water for more than 10 days. Moreover, the size of shells, surface area and pore volume were also decreased with the increase of pre-dropping lignin mass concentration. Hollow spherical structure of lignin nanoparticles with a hole on the surface was observed by TEM and SEM. The test result of UV-vis, XRD and FTIR showed that DOX could be loaded by LHNPs. The behaviors of DOX release were different in two pH systems. For the same test object, the drug released slightly rapidly in acidic(pH=5.5)condition comparing with in neutral(pH=7.4)condition. The larger specific surface area and porosity could improve the encapsulation ability of hollow nanoparticles for DOX, and the thicker shell particles had more stable controlled release result for DOX. Conclusion: The EHL could be microphase-separated in tetrahydrofuran and self-assembled into a dimensionally stable nano-scale surface with hollow spherical particles of a single pore. By controlling the initial mass concentration of lignin, it might be possible to obtain hollow particles of different diameters and shell wall thicknesses. For DOX@LHNPs, the larger the area and porosity is, the greater the drug loading. However, the hollow drug-loaded nanoparticles with more regular structure and thicker shell walls were beneficial to the stable release of DOX.

Key words: enzymatic hydrolysis lignin, lignin nanoparticles, structure, doxorubicin hydrochloride

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