Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites
© Zümreoglu-Karan et al; licensee Springer. 2011
Received: 25 July 2010
Accepted: 3 February 2011
Published: 3 February 2011
A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.
Magnetic iron oxide nanoparticles have attracted extensive attention in biomedicine and nanotechnology areas [1, 2]. Among them, hematite (α-Fe2O3) is the oldest known, most stable, and cheapest iron oxide with n-type semiconducting and soft magnetic properties . Since the report of Matijevic and co-workers in the early 1980s , much progress has been made toward the synthesis of monodisperse hematite particles with many different shapes that offer promising uses in water splitting, photocatalysis, photoelectrochemistry, magnetic recording media, and other nanodevices [5–7].
For practical applications, magnetic nanoparticles are coated with a protective shell to avoid agglomerization and for chemical stabilization . A nonmagnetic coating is generally employed not only for magnetic core stabilization but also for the integration of biofunctionalization . So far, many spherical core-shell magnetic nanostructures have been reported, while non-spherical core-shell particles with lower symmetries are relatively rare, although they would offer interesting physical properties. Ellipsoidal particles may serve as simple non-spherical models for studying anisotropic optoelectronic effects and drug delivery [10, 11]. There has been considerable interest in the synthesis and characterization of non-spherical hybrid nanostructures prepared by coating spindle-shaped hematite particles with gold , silica , titania , and polymeric shells .
LDHs have been introduced as alternative inorganic coating materials for magnetic nanoparticles . A number of magnetic core@LDH nanohybrids have been synthesized for catalysis [17, 18] and drug delivery [19–21] applications. We have recently reported anti-arthritic agent-carrying, nearly spherical core-shell magnesium ferrite@LDH nanocomposites that have a potential for magnetic arthritis therapy . In this communication, we describe an original morphology of such nanocomposites using spindle-shaped hematite as the core material and salicylate-intercalated Mg-Al-LDH as the shell.
Hematite nanoparticles were obtained by thermal decomposition of iron(III) oxalate in static air. Iron(III) oxalate was prepared hydrothermally by treating aqueous FeCl3 and H2C2O4 at pH 7 (adjusted by ammonia solution) for 48 h at 80°C in a pressure bomb in the presence of a cationic surfactant (cetyl tributyl ammonium bromide). The product was washed thoroughly several times with water and dried at room temperature. The powder was ground in an agate mortar and calcined at 300°C for 6 h.
Element analysis for metal ions was performed using a Spectro XLAP 2000 PRO XRF X-ray fluorescence spectrometer (Spectro Analytical Instruments GmbH) while for carbon and hydrogen on a varioMICRO CHNS instrument (Elementar Analysensysteme GmbH). The water content was determined by thermogravimetry on a DTG-60H (Shimadzu) thermal analysis system at a heating rate of 10°C/min. Powder X-ray diffraction patterns [XRD] were recorded using a D/MAX-2200 (Rigaku) diffractometer equipped with graphite-filtered Cu Kα radiation (λ = 1.54056 Å) from 3° to 70° (2θ) at a scanning rate of 4 min-1. Fourier transform infrared spectra [FTIR] were recorded in the range from 4,000 to 400 cm-1 on a Perkin Elmer Spectrum One instrument using the KBr pellet technique. The morphology and dimension of the synthesized products were observed with a FEI quanta 200 FEG (FEI Company) scanning electron microscope [SEM]. Transmission electron microscopy [TEM] and selected area electron diffraction [SAED] were performed using a FEI Tecnai G2 F30 (FEI Company) instrument operated at 300 or 100 kV. Magnetism of the products was measured at room temperature with a vibrating sample magnetometer (Quantum Designed Physical Property Measurement System (Quantum Design Inc.) in the magnetic field range of ±30 kOe. The electronic spectra were recorded on a Shimadzu UV-3600/UV-VIS-NIR Spectrophotometer (Shimadzu) equipped with a Praying Mantis attachment.
Results and discussion
Hematite particles were then coated with Mg-Al-NO3-LDH, as described previously for MgFe2O4@NO3-LDH . The XRD pattern of the as-prepared α-Fe2O3@NO3-LDH nanohybrid displayed typical d 003 and d 006 reflections due to the presence of the LDH shell, while characteristic peaks of the core materials (indicated by an asterisk in Figure 1A) remained intact during the coating process. From the spacing for the d 003 reflection, the interlayer distance was calculated as 8.7 Å. α-Fe2O3@NO3-LDH particles were then treated with acetylsalicylic acid solution, which gave salicylate ions (SAL, C7H5O3) by hydrolysis at alkaline reaction conditions. As in vivo salicylate is approximately equipotent to aspirin , the exchange of interlayer nitrate ions with salicylate ions resulted in the formation of a new bio-nanohybrid: α-Fe2O3@SAL-LDH. Intercalation of salicylate into the LDH structure was clearly followed as the d 003 and d 006 reflections for the NO3-LDH disappeared; thereby, a new series of intense basal reflections at lower 2θ values appeared instead. The basal spacing of the LDH increased from 8.7 to 17.2 Å owing to the incorporation of the larger organic ion between the layers. Figure 1F shows the SAED pattern of the final nanocomposite. The pattern was solved and diffraction spots from the LDH phase were indicated by red arrows while those from the core phase indicated by white arrows, confirming that the core particles were covered by the LDH shell.
In conclusion, we present here the first example of a non-spherical magnetic core@LDH shell architecture. This new structural feature is similar to that of the Ring Nebula, displaying a unique resemblance of nano to macro. The reported anisotropic nanohybrid possesses a great structural tunability and may show unprecedented properties in shape-sensitive drug delivery/release  and nanophotonics applications.
We thank Prof. A. Temel for XRD analysis and H.U. SNTG for magnetization measurements.
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