Single Molecular Wells–Dawson‐Like Heterometallic Cluster for the In Situ Functionalization of Ordered Mesoporous Carbon: A T₁‐ and T₂‐Weighted Dual‐Mode Magnetic Resonance Imaging Agent and Drug Delivery System

Abstract

Developing a feasible way to prepare highly dispersed heterometallic nanoparticles incorporated in porous carbon composites is of significant importance for multifunctional materials. In this work, heterometallic γ-Fe 2 O 3 and GdPO 4 nanoparticles that are incorporated in ordered mesoporous carbon composites are facilely prepared by a one-pot in situ method using a Wells-Dawson-like cluster of [Fe 6 Gd 6 (μ 3 -O) 2 (CO 3 )(O 3 PPh) 6 (O 2 C t Bu) 18 ] ({Fe 6 Gd 6 P 6 } for short) as the precursor. It is verified that the γ-Fe 2 O 3 and GdPO 4 nanoparticles are highly dispersed and embedded into the carbon matrix with a particle size smaller than 5 nm, even when the carbon matrix is changed from 2D hexagonal P6mm to 3D body-centered cubic Im-3m symmetry. Additionally, a formation mechanism is proposed. Furthermore, dual-mode magnetic resonance (MR) imaging and drug carrier properties are evaluated by in vitro experiments, which show a satisfactory T 1 -and T 2 -weighted MR imaging effect with r 1 and r 2 relaxivity values of 2.7 and 183.7 mM −1 s −1 , respectively, and doxorubicin hydrochloride carrier amount of 102 mg g −1 , identifying a combined function for potential diagnostic and therapy.

Mesoporous carbon nanomaterials in drug delivery and biomedical application

“…Magnetic resonance (MR) imaging is a widely used biomedical tool that is capable to noninvasively obtain anatomic information with high spatial and temporal resolution (Hricak, 2005 ). The MRI imaging of MCNs was mostly realized by embedding certain inorganic NPs into the carbonaceous structure, such as adolinium (Gd) chelates (Zhang et al., 2017b ), Fe 3 O 4 and manganese oxide (Zhang et al., 2015b ). Zhang et al.…”

Structure–Activity Relationship for the Catalytic Hydrogenation of Nitrobenzene by Single Platinum Atoms Supported on Nitrogen-Doped Carbon

“…Carbon-based materials have attracted much attention in the field of heterogeneous catalysis, energy storage, sensors, and drug-delivery platforms, thanks to their high surface area, good electrical conductivity, excellent chemical stability, and low price. − When carbon materials were utilized as the support for nanoparticles (NPs) and/or drug molecules, the performance of these hybrids could be promoted remarkably compared to their separated partners. − However, the dispersion and/or stability of these NPs and/or drug molecules over raw carbon support was poor, which might be attributed to the perfect electrical structure of carbon atoms. , …”

Hollow carbon nanospheres embedded with stoichiometric γ-Fe2O3 and GdPO4: tuning the nanospheres for in vitro and in vivo size effect evaluation

“… 33,34 Our groups previously developed a serial of functionalized magnetic carbon materials using post-synthetic modification with Wells–Dawson-like heterometallic clusters {Fe 6 Gd 6 P 6 }, which possessed T 1 and T 2 MRI enhanced capabilities. 35,36 In this context, MRI nanoagents of γ-Fe 2 O 3 and GdPO 4 nanoparticles were embedded into HCSs making it feasible to evaluate the size effect in vivo by MRI tracking.…”