Iron Oxide Nanomaterials at Interfaces for Sustainable Environmental Applications

IF 14 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of materials research Pub Date : 2024-07-03 DOI:10.1021/accountsmr.4c0015110.1021/accountsmr.4c00151
Mandeep Singh Bakshi*, 
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Abstract

Surface active iron oxide nanoparticles (NPs) belong to a novel class of nanomaterials with an inherent ability to adsorb at interfaces and perform diverse applications. Over the last several years, bulk soluble iron oxide NPs have emerged as one of the most prominent materials for environmental and biological applications. Bulk solubility unintentionally contributes toward the toxicity of nanomaterials with largely unknown consequences. Surface active NPs provide a viable solution and limit the toxicity by restricting their action to the interface. That enhances their applicability in the extraction processes across the immiscible interfaces frequently used in water purification as well as in biological systems. This Account summarizes the characteristic features of these applications elegantly accomplished by the surface active iron oxide NPs without even being incorporated in the aqueous bulk.

Surface activity of iron oxide NPs is achieved through hydrothermal synthesis by carefully selecting ionic Gemini surfactants that meticulously control crystal growth as well as provide colloidal stabilization. Both headgroup polarity and hydrophobicity of Gemini surfactants adsorbed on the surface of magnetic NPs are instrumental in generating precise surface activity, which mainly depends on the appropriate hydrophilic–lipophilic balance (HLB). Such a protocol produces highly surface active small crystalline iron oxide NPs of ∼10 nm functionalized with Gemini surfactants that only adsorb at immiscible interface and do not incorporate in bulk.

Surface active iron oxide NPs efficiently extract Au and Ag NPs as model nanometallic pollutants from aqueous bulk, which are otherwise difficult to extract by conventional filtration techniques. Extraction can be accomplished through specific and host–guest interactions operating between functionalized surface active magnetic NPs and nanometallic pollutants. Gemini surfactant functionalized magnetic NPs act as excellent vehicles for the extraction of protein fractions from aqueous bulk. Amphiphilicity of such NPs very well differentiates between the extraction efficiency of predominantly hydrophobic and hydrophilic protein fractions. Remarkably, magnetic NPs are also fully capable of extracting blood cells without inducing hemolytic anemia when functionalized with cyclodextrins (CD), which encapsulate sugar moieties of membrane proteins or the lipid bilayer of the cell membrane.

Extraction can be quantitatively monitored with simple techniques such as UV–visible and dynamic light scattering in real time. Highly sophisticated imaging and spectroscopic studies elucidate the mechanistic steps traced by the surface functionalities of both magnetic NPs and extracted species. Surface activity of magnetic NPs also makes their separation and quantification much easier under the effect of an external magnetic field for their reusability as sustainable nanomaterials. Separation of nanometallic pollutants and protein fractions from magnetic NPs can be achieved through vortex dispersion or pH variation, while ferromagnetism facilitates the rejuvenation of purified magnetic NPs to achieve sustainability. Thus, a novel class of surface active iron oxide NPs possesses enormous potential to explore their versatile and diverse interfacial chemistry that spans environmental to biological applications.

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用于可持续环境应用的界面氧化铁纳米材料
表面活性氧化铁纳米粒子(NPs)属于一类新型纳米材料,具有固有的界面吸附能力,可进行多种应用。在过去几年中,块状可溶性氧化铁 NPs 已成为环境和生物应用中最突出的材料之一。块状可溶性无意中造成了纳米材料的毒性,其后果在很大程度上是未知的。表面活性 NPs 提供了一种可行的解决方案,通过将其作用限制在界面上来限制毒性。这提高了它们在水净化和生物系统中常用的跨不溶界面萃取过程中的适用性。本报告总结了表面活性氧化铁 NPs 在不加入水体的情况下优雅地完成这些应用的特点。氧化铁 NPs 的表面活性是通过水热合成实现的,方法是精心选择离子型 Gemini 表面活性剂,这些表面活性剂能细致地控制晶体生长并提供胶体稳定性。磁性 NP 表面吸附的 Gemini 表面活性剂的头基极性和疏水性都有助于产生精确的表面活性,而表面活性主要取决于适当的亲水-亲油平衡(HLB)。表面活性氧化铁 NPs 能有效地从水体中萃取金、银 NPs 等模型纳米金属污染物,而传统的过滤技术很难萃取这些污染物。萃取可通过功能化表面活性磁性 NPs 与纳米金属污染物之间的特异性和主客体相互作用来实现。双子表面活性剂功能化磁性 NPs 是从水溶液中提取蛋白质的极佳载体。这种 NPs 的两亲性可以很好地区分主要疏水性和亲水性蛋白质馏分的萃取效率。值得注意的是,当磁性 NPs 与环糊精(CD)功能化时,也完全能够萃取血细胞而不会诱发溶血性贫血。高度复杂的成像和光谱研究可以阐明磁性 NPs 和提取物的表面功能所追踪的机理步骤。磁性 NPs 的表面活性还使其在外部磁场的作用下更容易分离和定量,从而使其成为可重复使用的可持续纳米材料。通过涡流分散或 pH 值变化,可以从磁性 NPs 中分离出纳米金属污染物和蛋白质馏分,而铁磁性则可使纯化的磁性 NPs 重新焕发活力,从而实现可持续性。因此,一类新型的表面活性氧化铁 NPs 具有巨大的潜力,可以探索其从环境到生物应用的多用途、多样化界面化学。
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