University of Maribor, Faculty of Mechanical Engineering, Institute of Engineering Materials and Design, Smetanova ulica 17, 2000 Maribor, Slovenia.
University of Ljubljana, Biotechnical Faculty, Department of Biology, Večna pot 111, 1000 Ljubljana, Slovenia.
Carbohydr Polym. 2023 Jul 1;311:120603. doi: 10.1016/j.carbpol.2023.120603. Epub 2023 Jan 21.
Dialdehyde cellulose nanofibrils (CNF) and nanocrystals (CNC) were prepared via periodate oxidation (CNF/CNC-ox) and subsequently functionalized with hexamethylenediamine (HMDA) via a Schiff-base reaction, resulting in partially crosslinked micro-sized (0.5-10 μm) particles (CNF/CNC-ox-HMDA) with an aggregation and sedimentation tendency in an aqueous media, as assessed by Dynamic Light Scattering and Scanning Electron Microscopy. The antibacterial efficacy, aquatic in vivo (to Daphnia magna) and human in vitro (to A594 lung cells) toxicities, and degradation profiles in composting soil of all forms of CNF/CNC were assessed to define their safety profile. CNF/CNC-ox-HMDA exhibited higher antibacterial activity than CNF/CNC-ox and higher against Gram-positive S. aureus than Gram-negative E. coli, yielding a bacteria reduction of >90 % after 24 h of exposure at the minimum (≤2 mg/mL), but potentially moderately/aquatic and low/human toxic concentrations (≥50 mg/L). The presence of anionic, un/protonated amino-hydrophobized groups in addition to unconjugated aldehydes of hydrodynamically smaller (<1 μm) CNC-ox-HMDA increased the reduction of both bacteria to log 9 at ≥4 mg/mL and their bactericidal activity. While only CNF/CNC-ox can be considered as biosafe and up to >80 % biodegradable within 24 weeks, this process was inhibited for the CNF/CNC-ox-HMDA. This indicated their different stability, application and disposal after use (composting vs. recycling).
通过过碘酸盐氧化制备了二醛纤维素纳米原纤维(CNF)和纳米晶体(CNC)(CNF/CNC-ox),然后通过席夫碱反应用己二胺(HMDA)进行功能化,得到部分交联的微尺寸(0.5-10 μm)颗粒(CNF/CNC-ox-HMDA),具有在水性介质中聚集和沉淀的趋势,这可以通过动态光散射和扫描电子显微镜评估。评估了所有形式的 CNF/CNC 的抗菌功效、水生体内(对大型溞)和人体体外(对 A594 肺细胞)毒性以及在堆肥土壤中的降解情况,以确定其安全性。CNF/CNC-ox-HMDA 表现出比 CNF/CNC-ox 更高的抗菌活性,对革兰氏阳性菌金黄色葡萄球菌的抑制作用比对革兰氏阴性菌大肠杆菌更强,在 24 小时的暴露时间内,最低(≤2 mg/mL)但潜在的中度/水生和低/人体毒性浓度(≥50 mg/L)下,细菌减少率超过 90%。除了未共轭的醛基之外,带负电荷的、未质子化的氨基疏水性基团存在于水动力较小的(<1 μm) CNC-ox-HMDA 中,增加了对数 9 的两种细菌的减少率,达到≥4 mg/mL 并具有杀菌活性。虽然只有 CNF/CNC-ox 可以被认为是生物安全的,并且在 24 周内可高达>80%可生物降解,但该过程被 CNF/CNC-ox-HMDA 抑制。这表明它们在使用后(堆肥与回收)具有不同的稳定性、应用和处理方式。