Mesoporous Magnetic/Polymer Hybrid Nanoabsorbent for Rapid and Efficient Removal of Heavy Metal Ions from Wastewater.

As an advanced water purification technology, magnetic nanoabsorbents are highly attractive for their sustainability, robustness, and energy efficiency. However, magnetic responsiveness and high adsorptive capacity are irreconcilable during the design and synthesis of a high-performance magnetic nanoabsorbent. Here, we address this issue by designing a kind of mesoporous magnetic polymer hybrid microspheres, where functional polymers such as polyrhodanine and polypyrrole were attached to the pore walls in the interior of mesoporous Fe3O4 microspheres through in situ polymerization. Due to the integrated large saturation magnetic moment, porous structure, and dense polymer layer, the mesoporous magnetic polymer hybrid microspheres demonstrated fast magnetic responsiveness, excellent recycling performance, and high adsorption capacities toward Pb(II) ions (189 mg g-1) for polyrhodanine and Cr(VI) ions (199 mg g-1) for polypyrrole. Furthermore, their potential application in wastewater treatment was verified by a self-made magnetic separation column, where the designed magnetic nanoabsorbent exhibits significant advantages including rapid separation of heavy metal ions and high outflow. This study provided a promising magnetic polymer hybrid nanoabsorbent for realizing efficient removal of heavy metal ions from wastewater.

Periodic Surface-Enhanced Raman Scattering-Encoded Magnetic Beads for Reliable Quantitative Surface-Enhanced Raman Scattering-Based Multiplex Bioassay.

Surface-enhanced Raman scattering (SERS)-based immunoassay on encoded beads is highly attractive with the advantages of ultrasensitivity, multiplex and high throughput. However, it was a great challenge to screen out in-focus signals of the immunoconjugated SERS nanoprobes on spherical bead conveniently. Here, periodic SERS-encoded magnetic beads (PSE-MBs) were developed through droplet optofluidic technique by using monodisperse SERS-encoded magnetic nanospheres as building blocks. The designed PSE-MBs not only exhibit huge coding capacity, but also provide the strongest and reproducible SERS coding signals as "in-focus beacons". When PSE-MBs are used as capture carriers in SERS-based immunoassay, both multiple target analytes and in-focus signals of SERS nanoprobes could be easily identified according to the collected SERS coding signals. Thus, reliable quantitative analysis of multiple target analytes could be conveniently achieved by such detection protocol. Additionally, the magnetic ingredient in PSE-MBs made the operation easily during the bioassay. The multiple advantages of PSE-MBs including large coding capacity, in-focus beacons and magnetic operation endorse them to be robust capture carriers in reliable quantitative SERS-based multiplex immunoassay.

Self-Template Etching Synthesis of Urchin-Like Fe3O4 Microspheres for Enhanced Heavy Metal Ions Removal.

Hierachical Fe3O4 microspheres with superparamagnetic properties are attractive for their superior structural, water-dispersible, and magnetic separation merits. Here self-template etching route was developed to create optimal porous structure in superparamagnetic Fe3O4 microspheres by using the oxalic acid (H2C2O4) as etching agent. A plausible formation mechanism of the urchin-like Fe3O4 microspheres was proposed based on systematic investigation of the etching process, which involved two stages including pore-forming step based on size-selective etching and pore-expanding step based on further etching. The as-synthesized Fe3O4 microspheres exhibited urchin-like structure with specific surface area and pore-size tunable, water-dispersible, and superparamagnetic properties. The optimal urchin-like Fe3O4 microspheres demonstrated superior performance including fast magnetic separation and high removal capabilities for the heavy metals ions like Pb2+ (112.8 mg g-1) and Cr(VI) (68.7 mg g-1). This work will shed new light on the synthesis of urchin-like microspheres for superior performance.

Highly Sensitive and Reproducible SERS Performance from Uniform Film Assembled by Magnetic Noble Metal Composite Microspheres.

To realize highly sensitive and reproducible SERS performance, a new route was put forward to construct uniform SERS film by using magnetic composite microspheres. In the experiment, monodisperse Fe3O4@SiO2@Ag microspheres with hierarchical surface were developed and used as building block of SERS substrate, which not only realized fast capturing analyte through dispersion and collection under external magnet but also could be built into uniform film through magnetically induced self-assembly. By using R6G as probe molecule, the as-obtained uniform film exhibited great improvement on SERS performance in both sensitivity and reproducibility when compared with nonuniform film, demonstrating the perfect integration of high sensitivity of hierarchal noble metal microspheres and high reproducibility of ordered microspheres array. Furthermore, the as-obtained product was used to detect pesticide thiram and also exhibited excellent SERS performance for trace detection.

Self-template synthesis of mesoporous and biodegradable Fe3O4 nanospheres as multifunctional nanoplatform for cancer therapy.

Superparamagnetic Fe3O4 nanospheres have demonstrated great potential as important components in nanomedicine for cancer imaging and therapy. One of the major obstacles that impedes their application is the slow degradation of ingested Fe3O4 nanospheres, which potentially causes long-term health risks. To tackle this issue, we proposed to fabricate Fe3O4 nanospheres with mesoporous structure via a simple self-template etching method. The mesoporous Fe3O4 nanospheres not only offered large specific surface area and weak-acidic responsive degradability, but also exhibited T2-weighted magnetic resonance contrast enhancement and magnetic targeting, which made them possible to serve as excellent cancer therapeutic nanoplatform. Both inorganic photothermal therapeutic Au nanoparticles and organic chemotherapeutic doxorubicin hydrochloride were demonstrated to be successfully loaded onto such kind of nanoplatform, and the hybrid nanomedicine demonstrated synergistic photothermal and chemotherapeutic activity for tumor elimination under near infrared irradiation and improved biodegradability in weak acidic tumor microenvironment. We believe that this study paved a simple way for designing multifunctional Fe3O4-based biodegradable nanomedicine.

Design of Raman reporter-embedded magnetic/plasmonic hybrid nanostirrers for reliable microfluidic SERS biosensors.

Magnetic-based microfluidic SERS biosensors hold great potential in various biological analyses due to their integrated advantages including easy manipulation, miniaturization and ultrasensitivity. However, it remains challenging to collect reliable SERS nanoprobe signals for quantitative analysis due to the irregular aggregation of magnetic carriers in a microfluidic chamber. Here, magnetic/plasmonic hybrid nanostirrers embedded with a Raman reporter are developed as capture carriers to improve the reliability of microfluidic SERS biosensors. Experimental results revealed that SERS signals from magnetic hybrid nanostirrers could serve as microenvironment beacons of their irregular aggregation, and a signal filtering method was proposed through exploring the relationship between the intensity range of beacons and the signal reproducibility of SERS nanoprobes using interleukin 6 as a model target analyte. Using the signal filtering method, reliable SERS nanoprobe signals with high reproducibility could be picked out from similar microenvironments according to their beacon intensity, and then the influence of irregular aggregation of magnetic carriers on the SERS nanoprobe could be eliminated. The filtered SERS nanoprobe signals also exhibited excellent repeatability from independent tests, which lay a solid foundation for a reliable working curve and subsequent accurate bioassay. This study provides a simple but promising route for reliable microfluidic SERS biosensors, which will further promote their practical application in biological analysis.

Hollow Prussian Blue Nanospheres for Photothermal/Chemo-Synergistic Therapy.

BACKGROUND: The integration of NIR photothermal therapy and chemotherapy is considered as a promising technique for future cancer therapy. Hollow Prussian nanospheres have attracted much attention due to excellent near-infrared photothermal conversion effect and drug-loading capability within an empty cavity. However, to date, the hollow Prussian nanospheres have been prepared by a complex procedure or in organic media, and their shell thickness and size cannot be controlled. Thus, a simple and controllable route is highly desirable to synthesize hollow Prussian nanospheres with controllable parameters. MATERIALS AND METHODS: Here, in our designed synthesis route, the traditional FeCl3 precursor was replaced with Fe2O3 nanospheres, and then the Prussian blue (PB) nanoparticles were engineered into hollow-structured PB (HPB) nanospheres through an interface reaction, where the Fe2O3 colloidal template provides Fe3+ ions. The reaction mechanism and control factors of HPB nanospheres were systematically investigated. Both in vitro and in vivo biological effects of the as-synthesized HPB nanospheres were evaluated in detail. RESULTS: Through systematical experiments, a solvent-mediated interface reaction mechanism was put forward, and the parameters of HPB nanospheres could be easily adjusted by growth time and template size under optimal water and ethanol ratio. The in vitro tests show the rapid and remarkable photothermal effects of the as-prepared HPB nanospheres under NIR laser irradiation (808 nm). Meanwhile, HPB nanospheres also demonstrated a high DOX loading capacity of 440 mg g-1 as a drug carrier, and the release of the drug can be regulated by the heat from PB shell under the exposure of an NIR laser. The in vivo experiments confirmed the outstanding performance of HPB nanospheres in photothermal/chemo-synergistic therapy of cancer. CONCLUSION: A solvent-mediated template route was developed to synthesize hollow Prussian blue (HPB) nanospheres in a simple and controllable way. The in vitro and in vivo results demonstrate the as-synthesized HPB nanospheres as a promising candidate due to their low toxicity and high efficiency for cancer therapy.

Magnetic Assembly Route to Construct Reproducible and Recyclable SERS Substrate.

The fabrication of a uniform array film through assembly of colloidal building blocks is of practical interest for the integrated individual and collective functions. Here, a magnetic assembly route was put forward to organize monodisperse noble metal microspheres into a uniform array film for surface-enhanced Raman scattering (SERS) application, which demonstrated the integrated signal sensitivity of single noble metal microspheres and reproducibility of their assembled uniform array film. For this purpose, monodisperse multifunctional Fe3O4@SiO2@TiO2@Ag (FOSTA) colloidal microspheres as building blocks were successfully synthesized through a homemade ultrasonic-assisted reaction system. When used in SERS test, these multifunctional microspheres could firstly bind the analyte (R6G) from solution and then assembled into a uniform film under an external magnetic field, which exhibited high SERS detection sensitivity with good reproducibility. In addition, due to the TiO2 interlayer in FOSTA colloidal microspheres, the building blocks could be recycled and self cleaned through photocatalytic degradation of the adsorbed analyte for recycling SERS application.

Chemical template-assisted synthesis of monodisperse rattle-type Fe3O4@C hollow microspheres as drug carrier.

A chemical template strategy was put forward to synthesize monodisperse rattle-type magnetic carbon (Fe3O4@C) hollow microspheres. During the synthesis procedure, monodisperse Fe2O3 microspheres were used as chemical template, which released Fe3+ ions in acidic solution and initiated the in-situ polymerization of pyrrole into polypyrrole (PPy) shell. With the continual acidic etching of Fe2O3 microspheres, rattle-type Fe2O3@PPy microspheres were generated with the cavity appearing between the PPy shell and left Fe2O3 core, which were then transformed into Fe3O4@C hollow microspheres through calcination in nitrogen atmosphere. Compared with traditional physical template, the shell and cavity of rattle-type hollow microspheres were generated in one step using the chemical template method, which obviously saved the complex procedures including the coating and removal of middle shells. The experimental results exhibited that the rattle-type Fe3O4@C hollow microspheres with different parameters could be regulated through controlled synthesis of the intermediate Fe2O3@PPy product. Moreover, when the rattle-type Fe3O4@C hollow microspheres were investigated as drug carrier, they manifested sustained-release behaviour of doxorubicin, justifying their promising applications as carriers in drug delivery. STATEMENT OF SIGNIFICANCE: The aim of the present study was first to synthesize rattle-type Fe3O4@C hollow microspheres through a simple synthesis method as a drug carrier. Here a chemical template synthesis of rattle-type hollow microspheres was developed, which saved the complex procedures including the coating and removal of middle shells in traditional physical template. Second, all the influence factors in the reaction processes were systematically investigated to obtain rattle-type Fe3O4@C hollow microspheres with controlled parameters. Third, the rattle-type Fe3O4@C hollow microspheres were studied as drug carriers and the influences of their structural parameters on drug loading and releasing performance were investigated.

Template-etching route to construct uniform rattle-type Fe3O4@SiO2 hollow microspheres as drug carrier.

Template-etching strategy was put forward to synthesize rattle-type magnetic silica (Fe3O4@SiO2) hollow microspheres in a controlled way. During the experiment, monodisperse Fe2O3 microspheres were fabricated as physical template to generate uniform Fe2O3@SiO2 with controlled shell thicknesses through sol-gel method, and the subsequent Fe2O3 template etching process created variable space between Fe2O3 core and SiO2 shell, and the final calcination process transformed rattle-type Fe2O3@SiO2 hollow microspheres into corresponding Fe3O4@SiO2 product in hydrogen/nitrogen atmosphere. Compared with traditional physical template, here template-etching synthesis of rattle-type hollow microspheres saved the insertion of middle shells and their removal, which simplified the synthesis process with controllable core size and shell thickness. The rattle-type Fe3O4@SiO2 hollow microspheres as drug carrier show efficient doxorubicin (DOX) loading, and the release rate of DOX loaded the rattle-type Fe3O4@SiO2 hollow microspheres exhibit a surprising shell-thickness-dependent and a pH responsive drug release features. Additionally, MTT assays in HeLa cells demonstrated that the Fe3O4@SiO2 nanocarriers were non-toxic even at the concentration of 250µgmL-1 for 48h. Thus, our results revealed that the Fe3O4@SiO2-DOX could play an important role in the development of intracellular delivery nanodevices for cancer therapy.

The template-assisted synthesis of polypyrrole hollow microspheres with a double-shelled structure.

Double-shelled polypyrrole hollow microspheres were synthesized via a novel template-assisted concept, using iron oxide hollow microspheres as both the sacrificial template and initiator in acidic solution.