Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Department of Environmental Science, Zhejiang University, Hangzhou 310058, China.
Zhejiang University-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou 311200, China.
Proc Natl Acad Sci U S A. 2024 Sep 3;121(36):e2409955121. doi: 10.1073/pnas.2409955121. Epub 2024 Aug 27.
Facing complex and variable emerging antibiotic pollutants, the traditional development of functional materials is a "trial-and-error" process based on physicochemical principles, where laborious steps and long timescales make it difficult to accelerate technical breakthroughs. Notably, natural biomolecular coronas derived from highly tolerant organisms under significant contamination scenarios can be used in conjunction with nanotechnology to tackling emerging contaminants of concern. Here, super worms () with high pollutant tolerance were integrated with nano-zero valent iron (nZVI) to effectively reduce the content of 17 antibiotics in wastewater within 7 d. Inspired by the synergistic remediation, nZVI-augmented worms were constructed as biological nanocomposites. Neither nZVI (0.3 to 3 g/L) nor worms (10 to 10 per liter) alone efficiently degraded florfenicol (FF, as a representative antibiotic), while their composite removed 87% of FF (3 μmol/L). Under antibiotic exposure, biomolecules secreted by worms formed a corona on and modified the nZVI particle surface, enabling the nano-bio interface greater functionality, including responsiveness, enrichment, and reduction. Mechanistically, FF exposure activated glucose-alanine cycle pathways that synthesize organic acids and amines as major metabolites, which were assembled into vesicles and secreted, thereby interacting with nZVI in a biologically response design strategy. Lactic acid and urea formed hydrogen bonds with FF, enriched analyte presence at the heterogeneous interface. Succinic and lactic acids corroded the nZVI passivation layer and promoted electron transfer through surface conjugation. This unique strategy highlights biomolecular coronas as a complex resource to augment nano-enabled technologies and will provide shortcuts for rational manipulation of nanomaterial surfaces with coordinated multifunctionalities.
面对复杂多变的新兴抗生素污染物,传统的功能材料开发是基于物理化学原理的“试错”过程,其中繁琐的步骤和较长的时间尺度使得技术突破难以加速。值得注意的是,源自高耐受生物在重大污染情况下衍生的天然生物分子冠,可以与纳米技术结合,用于处理新兴关注污染物。在这里,具有高污染物耐受能力的超级蠕虫()与纳米零价铁(nZVI)结合,可在 7 天内有效降低废水中 17 种抗生素的含量。受协同修复的启发,构建了增强型 nZVI 蠕虫的生物纳米复合材料。单独的 nZVI(0.3 至 3 g/L)或蠕虫(每升 10 至 10 个)都不能有效地降解氟苯尼考(FF,作为代表性抗生素),而它们的复合材料则能去除 87%的 FF(3 μmol/L)。在抗生素暴露下,蠕虫分泌的生物分子在 nZVI 颗粒表面形成冠并修饰其表面,使纳米-生物界面具有更大的功能,包括响应性、富集性和还原性。从机制上讲,FF 暴露激活了合成有机酸和胺作为主要代谢物的葡萄糖-丙氨酸循环途径,这些代谢物被组装成囊泡并分泌出来,从而以生物响应设计策略与 nZVI 相互作用。乳酸和尿素与 FF 形成氢键,在非均相界面富集分析物。琥珀酸和乳酸腐蚀 nZVI 的钝化层,并通过表面共轭促进电子转移。这种独特的策略突出了生物分子冠作为增强纳米技术的复杂资源的作用,并将为合理操纵具有协调多功能性的纳米材料表面提供捷径。