Fabrication of Novel Magnetic Nanoparticles of Multifunctionality for Water Decontamination

Efficient and powerful water purifiers are in increasing need because we are facing a more and more serious problem of water pollution. Here, we demonstrate the design of versatile magnetic nanoadsorbents (M-QAC) that exhibit excellent disinfection and adsorption performances at the same time. The M-QAC is constructed by a Fe₃O₄ core surrounded by a polyethylenimine-derived corona. When dispersed in water, the M-QAC particles are able to interact simultaneously with multiple contaminants, including pathogens and heavy metallic cations and anions, in minutes. Subsequently, the M-QACs along with those contaminants can be easily removed and recollected by using a magnet. Meanwhile, the mechanisms of disinfection are investigated by using TEM and SEM, and the adsorption mechanisms are analyzed by XPS. In a practical application, M-QACs are applied to polluted river water 8000-fold greater in mass, producing clean water with the concentrations of all major pollutants below the drinking water standard of China. The adsorption ability of M-QAC could be regenerated for continuous use in a facile manner. With more virtues, such as low-cost fabrication and easy scaling up, the M-QAC have been shown to be a very promising multifunctional water purifier with rational design and to have great potential for real water purification applications

Interaction between Organic Compounds and Catalyst Steers the Oxidation Pathway and Mechanism in the Iron Oxide-Based Heterogeneous Fenton System

In the past decades, extensive efforts have been devoted to the mechanistic understanding of various heterogeneous Fenton reactions. Nevertheless, controversy still remains on the oxidation mechanism/pathway toward different organic compounds in the classical iron oxide-based Fenton reaction, largely because the role of the interaction between the organic compounds and the catalyst has been scarcely considered. Here, we revisited the classic heterogeneous ferrihydrite (Fhy)/H2O2 system toward different organic compounds on the basis of a series of degradation experiments, alcohol quenching experiments, theoretical modeling, and intermediate analysis. The Fhy/H2O2 system exhibited highly selective oxidation toward the group of compounds that bear carboxyl groups, which tend to complex with the surface Fe(III) sites of the Fhy catalyst. Such interaction results in a nonradical inner sphere electron transfer process, which seizes one electron from the target compound and features negligible inhibition by the radical quencher. In contrast, for the oxidation of organic compounds that could not complex with the catalyst, the traditional HO· process makes the main contribution, which proceeds via hydroxyl addition reaction and could be readily suppressed by the radical quencher. This study implies that the interaction between the organic compounds and the catalyst plays a decisive role in the oxidation pathway and mechanism of the target compounds and provides a holistic understanding on the iron oxide-based heterogeneous Fenton system

Structure Evolution of Iron (Hydr)oxides under Nanoconfinement and Its Implication for Water Treatment

In the development of nanoenabled technologies for large-scale water treatment, immobilizing nanosized functional materials into the confined space of suitable substrates is one of the most effective strategies. However, the intrinsic effects of nanoconfinement on the decontamination performance of nanomaterials, particularly in terms of structural modulation, are rarely unveiled. Herein, we investigate the structure evolution and decontamination performance of iron (hydr)­oxide nanoparticles, a widely used material for water treatment, when confined in track-etched (TE) membranes with channel sizes varying from 200 to 20 nm. Nanoconfinement drives phase transformation from ferrihydrite to goethite, rather than to hematite occurring in bulk systems, and the increase in the nanoconfinement degree from 200 to 20 nm leads to a significant drop in the fraction of the goethite phase within the aged products (from 41% to 0%). The nanoconfinement configuration is believed to greatly slow down the phase transformation kinetics, thereby preserving the specific adsorption of ferrihydrite toward As­(V) even after 20-day aging at 343 K. This study unravels the structure evolution of confined iron hydroxide nanoparticles and provides new insights into the temporospatial effects of nanoconfinement on improving the water decontamination performance

Fluorous Cylindrical Micelles of Controlled Length by Crystallization-Driven Self-Assembly of Block Copolymers in Fluorinated Media

Fluorous solvents have recently found broad applications in medical treatments as well as catalytic transformations, yet the controlled self-assembly of nanomaterials in fluorinated media has remained a challenge. Herein, we report the synthesis of block copolymers containing a crystalline polyferrocenylsilane metalloblock and a highly fluorinated coil block and their controlled self-assembly in fluorinated media. Using the crystallization-driven self-assembly approach, cylindrical micelles have been prepared with controlled lengths and narrow length polydispersities by self-seeding. Finally, by partial functionalization of these block copolymers with fluorescent dye molecules, we show that well-defined, functional nanomaterials can be obtained in the fluorous phase

Polyferrocenylsilane Crystals in Nanoconfinement: Fragmentation, Dissolution, and Regrowth of Cylindrical Block Copolymer Micelles with a Crystalline Core

Two samples of rod-like micelles in decane were prepared by seeded growth from a sample of a poly­(isoprene-<i>b</i>-ferrocenyldimethylsilane) diblock copolymer (PI₁₀₀₀–PFS₅₀, where the subscripts indicate the degree of polymerization). These micelles were uniform in length with a mass/length of 1.9 molecules/nm. The longer micelles (L-1250) had a number-average length <i>L</i>_n = 1243 nm, whereas the shorter micelles (L-250) had <i>L</i>_n = 256 nm. We used transmission electron microscopy (TEM) to examine the behavior of these micelles when dilute solutions of L-1250 or L-250 or their mixtures were heated at temperatures ranging from 40 to 75 °C and then cooled to room temperature. At 55 °C, the L-1250 sample underwent kinetically controlled fragmentation to give a broad distribution of micelle lengths. At this temperature, fragmentation was much less prominent in the L-250 sample. At higher temperatures, micelles with narrow distributions of lengths were obtained in each case (<i>L</i>_w/<i>L</i>_n ≈ 1.01). This process operates under thermodynamic control, and <i>L</i>_n values increased strongly with an increase in temperature. These results indicate that the micelles fragment, and polymer molecules dissolve, as the samples were heated. The fraction of surviving fragments decreased significantly at elevated temperatures, presumably reflecting a distribution of crystallinity in the cores of the micelle precursor. When the solutions were cooled, the surviving fragments served as seeds for the epitaxial growth of the micelles as the polymer solubility decreased. The most striking result of these experiments was the finding that fragments formed from the L-1250 micelles had a distribution of dissolution temperatures shifted by about 5 °C to higher temperature than the shorter L-250 micelles

Highly Efficient Water Decontamination by Using Sub-10 nm FeOOH Confined within Millimeter-Sized Mesoporous Polystyrene Beads

Millimeter-sized polymer-based FeOOH nanoparticles (NPs) provide a promising option to overcome the bottlenecks of direct use of NPs in scaled-up water purification, and decreasing the NP size below 10 nm is expected to improve the decontamination efficiency of the polymeric nanocomposites due to the size and surface effect. However, it is still challenging to control the dwelled FeOOH NP sizes to sub-10 nm, mainly due to the wide pore size distribution of the currently available polymeric hosts. Herein, we synthesized mesoporous polystyrene beads (MesoPS) via flash freezing to assemble FeOOH NPs. The embedded NPs feature with α-crystal form, tunable size ranging from 7.3 to 2.0 nm and narrow size distribution. Adsorption of As­(III/V) by the resultant nanocomposites was greatly enhanced over the α-FeOOH NPs of 18 × 60 nm, with the iron mass normalized capacity of As­(V) increasing to 10.3 to 14.8 fold over the bulky NPs. Higher density of the surface hydroxyl groups of the embedded NPs as well as their stronger affinity toward As­(V) was proved to contribute to such favorable effect. Additionally, the as-obtained nanocomposites could be efficiently regenerated for cyclic runs. We believe this study will shed new light on how to fabricate highly efficient nanocomposites for water decontamination

Evolving Role of Ca²⁺ on the Long-Term Phosphate Adsorption-Regeneration Performance of Nanoconfined Hydrated Lanthanum Oxides: Short-Term Enhancement and Long-Term Inhibition

Phosphorus (P) advanced treatment by adsorption reduces the risk of eutrophication in natural waters and reservoirs. The impact of ubiquitous Ca2+ on long-term P removal is critical in assessing the regeneration efficiency of one adsorbent, which is a vital indicator for cost-effectiveness. Given the critical role of lanthanum (La)-based composite materials in P removal, in this study, we unravel the long-term evolving role of Ca2+ on phosphate removal by nanosized hydrated lanthanum oxides (HLO) confined in cross-linked polystyrene beads (HLO@201) over 20 adsorption-regeneration cycles and fixed-bed column runs, with a combination of macroscopic adsorption experiments, microscopic structural investigation, and theoretical calculations. The role of Ca2+ gradually evolves from positive (5–70% higher than Ca2+-free group) to negative (18–41% lower than the Ca2+-free group) with ongoing cyclic runs of HLO@201, which is distinctive from the bulky HLO. The presence of Ca2+ enhances P uptake by HLO@201 possibly through La–P–Ca–P multiple complexation and Ca–P precipitation (i.e., hydroxyapatite, HAP) inside the polymeric host, which creates an antagonistic effect with HLO over time. The formed Ca–P precipitates may accumulate and encapsulate on the surface of HLO nanoparticles, which induce the formation of irreversible LaPO4·xH2O under nanoconfinement that deplete the active adsorptive sites. A two-step (acid wash + NaOH) regeneration method can partially recover the P removal performance of HLO@201. We envision that this study could be a cautionary tale for advanced treatment of P by adsorption, to inspire re-evaluation on the long-term performance of adsorption processes

Effective Drug Carrier Based on Polyethylenimine-Functionalized Bacterial Cellulose with Controllable Release Properties

The development of low-cost biological materials with controlled drug release profile is of great importance but challenging in pharmaceutical industry. Recently, bacterial cellulose nanofibers have provoked intensive research interests in tissue engineering and the pharmaceutical science due to their stability, availability, sustainability, and low toxicity. Here we describe the development of a PEI (polyethylenimine)-grafted bacterial cellulose (BC) as an efficient drug delivery system. The PEI-BC aerogels were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and zeta potential measurements. The optimum sample exhibited enhanced mechanical strength, remarkable adsorption capacity toward aspirin, BSA, and gentamicin, prolonged and pH-dependent drug release, and low cytotoxicity. Our work has presented a rational structure design from biomass for controllable drug carrier

Uniform, High Aspect Ratio Fiber-like Micelles and Block Co-micelles with a Crystalline π‑Conjugated Polythiophene Core by Self-Seeding

Monodisperse fiber-like micelles with a crystalline π-conjugated poly­thiophene core with lengths up to ca. 700 nm were successfully prepared from the diblock co­polymer poly­(3-hexyl­thiophene)-<i>block</i>-poly­styrene using a one-dimensional self-seeding technique. Addition of a poly­thiophene block co­polymer with a different corona-forming block to the resulting nanofibers led to the formation of segmented B-A-B triblock co-micelles by crystallization-driven seeded growth. The key to these advances appears to be the formation of a relatively defect-free crystalline micelle core under the self-seeding conditions

A High-Sensitivity Lanthanide Nanoparticle Reporter for Mass Cytometry: Tests on Microgels as a Proxy for Cells

This paper addresses the question of whether one can use lanthanide nanoparticles (e.g., NaHoF₄) to detect surface biomarkers expressed at low levels by mass cytometry. To avoid many of the complications of experiments on live or fixed cells, we carried out proof-of-concept experiments using aqueous microgels with a diameter on the order of 700 nm as a proxy for cells. These microgels were used to test whether nanoparticle (NP) reagents would allow the detection of as few as 100 proteins per “cell” in cell-by-cell assays. Streptavidin (SAv), which served as the model biomarker, was attached to the microgel in two different ways. Covalent coupling to surface carboxyls of the microgel led to large numbers (>10⁴) of proteins per microgel, whereas biotinylation of the microgel followed by exposure to SAv led to much smaller numbers of SAv per microgel. Using mass cytometry, we compared two biotin-containing reagents, which recognized and bound to the SAvs on the microgel. One was a metal chelating polymer (MCP), a biotin end-capped polyaspartamide containing 50 Tb³⁺ ions per probe. The other was a biotinylated NaHoF₄ NP containing 15 000 Ho atoms per probe. Nonspecific binding was determined with bovine serum albumin (BSA) conjugated microgels. The MCP was effective at detecting and quantifying SAvs on the microgel with covalently bound SAv (20 000 SAvs per microgel) but was unable to give a meaningful signal above that of the BSA-coated microgel for the samples with low levels of SAv. Here the NP reagent gave a signal 2 orders of magnitude stronger than that of the MCP and allowed detection of NPs ranging from 100 to 500 per microgel. Sensitivity was limited by the level of nonspecific adsorption. This proof of concept experiment demonstrates the enhanced sensitivity possible with NP reagents in cell-by-cell assays by mass cytometry