We report Periodic Mesoporous Ionosilica Nanoparticles (PMINPs) as versatile nano-objects for imaging, photodynamic therapy (PDT), and efficient adsorption and delivery of siRNA into breast cancer cells. In order to endow these nanoparticles PDT and siRNA photochemical internalization (PCI) properties, a porphyrin derivative was integrated into the ionosilica framework. For this purpose, we synthesized PMINPs via hydrolysis-cocondensation procedures from oligosilylated ammonium and porphyrin precursors. The formation of these nanoobjects was attested by TEM. The formed nanoparticles were then thoroughly characterized via solid state NMR, nitrogen sorption, DLS, UV-Vis and fluorescence spectroscopy. Our results indicate the formation of highly porous nanorods with a length of 108 ± 9 nm and a width of 54 ± 4 nm. A significant PDT effect of type I mechanism (95 ± 2.8% of cell death) was observed upon green light irradiation in nanoparticles treated-breast cancer cells, while the blue light irradiation caused a significant phototoxic effect in non-treated cells. Furthermore, PMINPs formed stable complexes with siRNA (up to 24 h), which were efficiently internalized into the cells after 4 h of incubation mostly with energy-dependent endocytosis process. The PCI effect was obvious with green light irradiation and successfully led to 83 ± 1.1% silencing of luciferase gene in luciferase expressing breast cancer cells, while no gene silencing effect was observed with blue light irradiation. The present work highlights the high potential of porphyrin-doped PMINPs as multifunctional nanocarriers for nucleic acids, such as siRNA, with a triple ability to perform imaging, PDT and PCI.
Functional
polymers, such as poly(ethylene glycol) (PEG), terminated
with a single phosphonic acid, hereafter PEG
ik-Ph are often applied to coat metal oxide surfaces during
post-synthesis steps but are not sufficient to stabilize sub-10 nm
particles in protein-rich biofluids. The instability is attributed
to the weak binding affinity of post-grafted phosphonic acid groups,
resulting in a gradual detachment of the polymers from the surface.
Here, we assess these polymers as coating agents using an alternative
route, namely, the one-step wet-chemical synthesis, where PEG
ik-Ph is introduced with cerium precursors
during the synthesis. Characterization of the coated cerium oxide
nanoparticles (CNPs) indicates a core–shell structure, where
the cores are 3 nm cerium oxide and the shell consists of functionalized
PEG polymers in a brush configuration. Results show that CNPs coated
with PEG1k-Ph and PEG2k-Ph are of potential
interest for applications as nanomedicines due to their high Ce(III)
content and increased colloidal stability in cell culture media. We
further demonstrate that the CNPs in the presence of hydrogen peroxide
show an additional absorbance band in the UV–vis spectrum,
which is attributed to Ce–O2
2– peroxo-complexes and could be used in the evaluation of their catalytic
activity for scavenging reactive oxygen species.
Periodic Mesoporous Ionosilica Nanoparticles (PMINPs) made via co‐condensation reactions starting from an ionosilica precursor and a porphyrin derivative were used for simultaneous BODIPY/siRNA delivery in cancer cells. We observed high BODIPY loading capacities and efficiencies of the PMINPs that are triggered by anion exchange. siRNA adsorption took place on the surface of the nanoparticles, whereas BODIPY was encapsulated within the core of the nanoparticles. BODIPY release was found to be pH‐dependent. Our results indicate 94 % BODIPY release after 16 h at pH 4, whereas only 2 % were released at pH 7.4. Furthermore, complexation with siRNA against luciferase gene was observed at the surface of PMINPs and gene silencing through its delivery via photochemical internalization (PCI) mechanism was efficient in MDA‐MB‐231 breast cancer cells expressing stable luciferase.
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