Prussian Blue Nanoparticles as Multienzyme Mimetics and Reactive Oxygen Species Scavengers.

The generation of reactive oxygen species (ROS) is an important mechanism of nanomaterial toxicity. We found that Prussian blue nanoparticles (PBNPs) can effectively scavenge ROS via multienzyme-like activity including peroxidase (POD), catalase (CAT), and superoxide dismutase (SOD) activity. Instead of producing hydroxyl radicals (•OH) through the Fenton reaction, PBNPs were shown to be POD mimetics that can inhibit •OH generation. We theorized for the first time that the multienzyme-like activities of PBNPs were likely caused by the abundant redox potentials of their different forms, making them efficient electron transporters. To study the ROS scavenging ability of PBNPs, a series of in vitro ROS-generating models was established using chemicals, UV irradiation, oxidized low-density lipoprotein, high glucose contents, and oxygen glucose deprivation and reperfusion. To demonstrate the ROS scavenging ability of PBNPs, an in vivo inflammation model was established using lipoproteins in Institute for Cancer Research (ICR) mice. The results indicated that PBNPs hold great potential for inhibiting or relieving injury induced by ROS in these pathological processes.

Prussian blue modified ferritin as peroxidase mimetics and its applications in biological detection.

Ferritins are natural nanoscale structures composed with 24 subunits endowed with similar three-dimensional structures. The iron is stored in the form of ferrihydrite phosphate in the hollow spherical ferritin shells. Prussian blue nanoparticles (PBNPs) have been certified a kind of mimetic enzyme with the advantages of stability, high catalytic activity and low prices. In this context, we designed a strategy to synthesize PBNPs of small size using ferritin as template and meanwhile retain the biological properties of ferritin. Our results show the resulting nanostructures (Prussian blue modified ferritin nanoparticles, PB-Ft NPs) got very small size and relatively high catalytic activity, furthermore, PB-Ft NPs successfully combined the intrinsic enzyme mimetic activity of PBNPs and the specificity of ferritin. Peroxidase-like activity which fits well the Michaelis-Menten kinetics was found strongly depending on pH, temperature and the concentration of PB-Ft NPs. Then a sensitive method for glucose detection was developed using glucose oxidase (GOx) and PB-Ft NPs. The consequence of Enzyme-linked immunosorbent assay (ELISA) shows PB-Ft NPs possess both specificity and peroxidase-like activity, which suggests that PB-Ft NPs can be served as a useful reagent in some biological detections.

Preparation and characterization of highly luminescent water-soluble CdTe quantum dots as optical temperature probes.

Highly luminescent water-soluble CdTe quantum dots were synthesized with an electrogenerated precursor. The size, morphology, optical properties as well as fluorescence stability were characterized by transmission electron microscope, high-resolution transmission electron microscope, powder X-ray diffraction, UV-vis-NIR spectrophotometer, and fluorescence spectrophotometer. The results show that the CdTe QDs with diameter ranging from 2.0 nm to 3.5 nm have good crystallizability, high quantum yield and favorable fluorescence stability. Moreover, the CdTe QDs demonstrate temperature-dependent reversible PL intensity variations at moderate temperatures above room temperature. It is also found that the QDs with different sizes possess different sensitivity to the temperature. All the studies indicate that the CdTe QDs are expected to be promising candidates for a variety of biological and biomedical applications.

Surface Modified Iron Oxide Nanoparticles as Fe Source Precursor to Induce the Formation of Prussian Blue Nanocubes.

Nano-sized Prussian blue (PB) cubes were synthesized at room temperature by simply stirring the mixture of surface modified iron oxide nanoparticles (IONPs) and potassium ferrocyanide in an aqueous acid solution. The nanocubes were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The influence of different molecules modified on the surface of IONPs on the cube formation was discussed. The surface modification with dimercaptosuccinic acid (DMSA), 3-aminopropyltriethoxysilane (APTS) and citric acid (CA) all displayed a key role in the formation precess of PB nanocubes, but which could not be formed as bare IONPs or Fe3+ were used as precursor. Combined with the reaction process tracing with UV-vis absorption spectroscopy and TEM, a possible kinetically controlled growth mechanism was proposed where slower formation rate of amorphous PB due to very low release rate of Fe ions from the surface modified IONPs and subsequent recrystallization are responsible for the obtained PB nanocubes. The peroxidase-like catalytic activity of the synthesized nanocubes was investigated and catalysis was found to follow Michaelis-Menten kinetics. The potential of using such PB nanocubes as an effective MRI contrast agent was also demonstrated.

Dual enzyme-like activities of iron oxide nanoparticles and their implication for diminishing cytotoxicity.

Iron oxide nanoparticles (IONPs) are frequently used in biomedical applications, yet their toxic potential is still a major concern. While most studies of biosafety focus on cellular responses after exposure to nanomaterials, little is reported to analyze reactions on the surface of nanoparticles as a source of cytotoxicity. Here we report that different intracellular microenvironment in which IONPs are located leads to contradictive outcomes in their abilities to produce free radicals. We first verified pH-dependent peroxidase-like and catalase-like activities of IONPs and investigated how they interact with hydrogen peroxide (H(2)O(2)) within cells. Results showed that IONPs had a concentration-dependent cytotoxicity on human glioma U251 cells, and they could enhance H(2)O(2)-induced cell damage dramatically. By conducting electron spin resonance spectroscopy experiments, we showed that both Fe(3)O(4) and γ-Fe(2)O(3) nanoparticles could catalyze H(2)O(2) to produce hydroxyl radicals in acidic lysosome mimic conditions, with relative potency Fe(3)O(4) > γ-Fe(2)O(3), which was consistent with their peroxidase-like activities. However, no hydroxyl radicals were observed in neutral cytosol mimic conditions with both nanoparticles. Instead, they decomposed H(2)O(2) into H(2)O and O(2) directly in this condition through catalase-like activities. Transmission electron micrographs revealed that IONPs located in lysosomes in cells, the acidic environment of which may contribute to hydroxyl radical production. This is the first study regarding cytotoxicity based on their enzyme-like activities. Since H(2)O(2) is continuously produced in cells, our data indicate that lysosome-escaped strategy for IONP delivery would be an efficient way to diminish long-term toxic potential.